Tapali PHD PDF

Department of Environmental and Natural Resources Management
AN INTEGRATED DESIGN PROCESS FOR

DURABLE CONCRETE STRUCTURES AT THE
MINIMUM ENVIRONMENTAL COST
APPLICATION WITH THE INCORPORATION
OF RICE HUSK ASH
PhD Dissertation
by
Julia G. Tapali
Civil Engineer, MSc.
Supervisor: Assoc. Prof. Vagelis G. Papadakis
Agrinio, Greece, 2014

J.G. Tapali
Although the author has done its best to ensure that any information given is accurate, no
liability or responsibility of any kind (including liability for negligence) is accepted in this
respect by the firm and the author. The reader should verify the applicability of the
information to particular situations and is urged to consult with appropriate professionals prior
to taking any action or making any interpretation that is within the realm of a professional
practice.
J.G. Tapali & University of Patras
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or by any means, electronic, mechanical, photocopying,
recording, or otherwise now known or hereafter invented, without the prior permission of the
author J.G. Tapali & University of Patras.
First published 2014
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PhD Dissertation
ADVISORY COMMITTEE
1. Vagelis G. Papadakis (Supervisor), Associate Professor, Department of Environmental
& Natural Resources Management, School of Engineering, University of Patras, Greece
2. Ioanna Papayianni, Professor, Department of Civil Engineering, School of Engineering,
Aristotle University of Thessaloniki, Greece
3. Stamatis Tsimas, Professor, School of Chemical Engineering, National Technical
University of Athens, Greece
EXAMINATIONAL COMMITTEE
1. Yiannis Deligiannakis, Professor, Department of Environmental & Natural Resources
Management, School of Engineering, University of Patras, Greece
2. Dimitrios Karamanis, Assistant Professor, Department of Environmental & Natural
Resources Management, School of Engineering, University of Patras, Greece
3. Angeliki Moutsatsou, Professor, School of Chemical Engineering, National Technical
4. Vagelis G. Papadakis, Associate Professor, Department of Environmental & Natural
Resources Management, School of Engineering, University of Patras, Greece
5. Ioanna Papayianni, Professor, Department of Civil Engineering, School of Engineering,
Aristotle University of Thessaloniki, Greece
6. Kosmas K. Sideris, Associate Professor, Department of Civil Engineering, School of
Engineering, Democritus University of Thrace, Greece
7. Stamatis Tsimas, Professor, School of Chemical Engineering, National Technical
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J.G. Tapali
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PhD Dissertation
Foreword
This PhD Dissertation is the result of an extensive research work and the end of a challenging trip that
lasted three and half years, from January of 2011 until June of 2014. The main reason that urged me to
start dealing with the specific subject was the fact that I felt we are all responsible for protecting the
environment in which we are living. As a civil engineer I also thought that I have an additional
responsibility towards both the social and scientific community, so I could not stay away from all the
processes taken place at a global level aiming at the establishment of a sustainable way of building.
Nowadays there is a great concern about the environmental footprint of constructions while the
principles of sustainable development have prevailed worldwide. Cement industry is responsible for a
considerable amount of CO2 emissions and unsatisfactory durability is a common case in reinforced
concrete structures. In particular, corrosion of steel reinforcement is the most serious durability
problem, caused by either carbonation or chloride diffusion. Concrete is considered to be the most
popular building material and it is estimated that its consumption will increase considerably in the next
years. Therefore, new strategies and techniques should be used to make cement and construction
industry a more environmentally friendly sector.
A great challenge nowadays is the construction of durable concrete structures which are friendly to the
environment and last longer. Towards achieving this target each involved party could play its own role
and therefore should undertake its own responsibilities. Governments should provide incentives to
engineers and manufactures to adopt new green methods and products. During the past decades
scientists are investigating innovative ways for reducing the environmental cost of constructions, such
as the utilisation of Supplementary Cementing Materials (SCM) in the concrete mix. By realizing the
high importance of all these crucial issues and the necessity to develop initiatives aiming at the
sustainable development of building sector, I decided to begin the elaboration of the present thesis,
after discussions with Assoc. Prof. Vagelis G. Papadakis.
The study focuses on the enhancement of the structure and potential of an existing software tool,
EUCON, developed by Papadakis et al which is based on proven mathematical models, in full
compliance with the European Standards for cement: EN 197 and concrete: EN 206. The
environmental aspects of designing the concrete mix are highlighted and introduced in this software
offering this way an Integrated Design Process (IDP) tool for reinforced concrete structures. The
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J.G. Tapali
valorisation of biomass ash and particularly rice husk ash (RHA) in the construction sector is
thoroughly analysed in the study and new types of concrete incorporating these types of agro-
industrial by-products are suggested, in order to achieve a balance between durability and
sustainability. In general, this work is addressed to Construction and Environmental Engineers in
addition to Building Material Manufacturers towards providing them a structured framework of
methodologies for designing durable reinforced concrete constructions at the minimum environmental
and economical cost and also an industrial ecology scheme for the sustainable development of the
cement and construction industry.
Assoc. Prof. V.G. Papadakis is heartfelt acknowledged for his significant contribution and constant
guidance as supervisor during the elaboration of my Ph.D. Dissertation. Grateful thanks are due to the
other two members of the Advisory Committee, Prof. S. Tsimas (National Technical University of
Athens) and Prof. I. Papayianni (Aristotle University of Thessaloniki) for evaluating my PhD
dissertation and providing their valuable remarks, comments and recommendations. TITAN Cement
Company S.A., Agrino EV.GE Pistiolas S.A., University of Porto and especially Prof. J. Coutinho are
also cordially acknowledged for their assistance in providing data and experimental results necessary
for the completion of the present study. I would also like to thank Dr. S. Demis (Invited Lecturer,
Department of Civil Engineering, University of Patras) for the successful cooperation we had,
especially during the preparation of the research publications in international journals and conferences.
Finally, I wish to express my great thanks to Sotiri, for the encouragement, patience and willingness to
support my effort in any possible way all this time, from the beginning of my PhD until the day that
these lines were written.
Julia G. Tapali
June 2014
Julia G. Tapali holds a diploma in Civil Engineering (2007) from the Aristotle University of
Thessaloniki, Greece, and a MSc. on Design, Organization and Management of Transport Systems
from the same Institution (2009). The Diploma Thesis of MSc. was elaborated at the University of
Piraeus on Funding for Greek and Greek-owned Shipping Companies. She is a Ph.D. candidate in the
Department of Environmental and Natural Resources Management, University of Patras on the subject
of Sustainable Development of the Building Sector - Estimation and Reduction Practices of the
Environmental Cost of Constructions, under the supevision of Assoc. Prof. V.G. Papadakis. She has
participated in a number of conferences and authored several papers. She worked on structural
analysis and design of steel structures at the construction company EKTE ATEVE (2007-2008). She
also worked as a consultant engineer on issues of renewable energy, at the company Project Epsilon,
in Thessaloniki (2012). At the present, she is a member of TSRG/AUTh (Transport Research Group
of Aristotle University of Thessaloniki) and participates as a Researcher in the SEE project ADB
Multiplatform (Adriatic-Danube-Black Sea Multimodal platform) which aims to develop and promote
environmentally friendly, multimodal transport solutions.
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PhD Dissertation
Contents
Page
FOREWORD 5
CONTENTS 7
ABSTRACT 11
ABSTRACT IN GREEK 15
1. INTRODUCTION 19
1.1 Brief description of the building sector 19
1.2 Environmental impacts of the building sector 22
1.2.1 Environmental cost components 23
1.2.2 Environmental impact of building materials 26
1.2.3 Reduction of the environmental cost 30
1.2.4 Towards a sustainable construction 32
1.3 Objectives and structure of the present thesis 37
1.3.1 Objectives of the present thesis 37
1.3.2 Innovative aspects of the thesis 39
1.3.3 Structure of the thesis 41
2. DURABILITY & SUSTAINABILITY OF CONCRETE CONSTRUCTIONS 45

2.1 Introduction 45
2.2 Concrete durability and the EN 206 approach 51
2.2.1 Limiting values for concrete composition 51
2.2.2 Performance-related design methods 52
2.3 Concrete mix design 54
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J.G. Tapali
2.3.1 Constituent materials for concrete composition 54

2.3.2 Design strategy 61
2.4 Concrete service life estimation tool 63
2.4.1 Modeling for carbonation exposure 65
2.4.2 Modeling for chloride ingress 67
2.4.3 Cost and environmental aspects 69
2.4.4 Validation and verification 71
2.5 Life cycle analysis for constructions 74
3. ENVIRONMENTAL COST OF CONCRETE PRODUCTION

ESTIMATION & OPTIMIZATION 77
3.1 Introduction 77
3.2 Estimation of environmental cost of concrete 80
3.3 Structured methodology for concrete mix design optimization 83
3.4 Utilization of structured methodology for concrete mix design optimization 85
3.4.1 Step 1: Selection of initial CCP values 85
3.4.2 Steps 2 and 3: Replacing aggregates or cement by SCM 86
3.4.3 Step 4: Further reduction of W and/or C contents 91
3.5 Discussion 94
4. INVESTIGATION ON THE EFFECTIVENESS OF BIOMASS ASHES

AS POZZOLANIC MATERIALS 99
4.1 Introduction 99
4.2 Types and evaluation methodology for biomass ashes 101
4.2.1 Types of biomass ashes investigated 101
4.2.2 Methodology followed for the evaluation of biomass ashes
as cementitious materials 104
4.3 Results of biomass ashes evaluation 105
4.3.1 Efficiency factors 106
4.3.2 Chloride penetration 108
4.4 Discussion 110
5. UTILIZATION OF RICE HUSK ASH IN THE BUILDING SECTOR

TECHNOECONOMICAL ANALYSIS AND
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ENVIRONMENTAL BENEFITS 117

5.1 Introduction 117
5.1.1 General 117
5.1.2 Present study 119
5.2 RHA derivatives for construction Production processes 121
5.2.1 Rice and RHA production 121
5.2.2 RHA derivatives 124
5.2.3 Flowchart for insulation materials production 126
5.2.4 Flowchart for pozzolanic materials production 129
5.2.5 Raw materials 131
5.3 Equipment, plant site and restrictions 134
5.3.1 Equipmenr for RHA conversion to pozzolanic material 134
5.3.2 Plant site 136
5.3.3 Restrictions 138
5.4 Organizational structure, fixed and operational cost 141
5.4.1 Organizational structure and personnel 141
5.4.2 Calculation of fixed costs and initial working capital 143
5.4.3 Calculation of the operational cost 145
5.5 Market, competition and sales 149
5.6 Cost-benefit analysis and evaluation 152
5.6.1 Expected profit 152
5.6.2 Evaluation of the investment 153
5.6.3 Sensitivity and risk analyses 154
5.6.4 Cost-benefit analysis for RHA valorisation as insulation material 158
5.7 Optimization and testing runs 163
5.7.1 Introduction 163
5.7.2 Testing program 164
5.7.3 Test results & discussion 168
5.7.4 Discussion and further suggestions 170
5.8 Environmental benefits 173
5.8.1 Estimation of concrete service life 173
5.8.2 Environmental impact of concrete 175
5.8.3 Discussion and conclusions 179
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J.G. Tapali
6. CONCLUSIONS 183
7. REFERENCES 189
CURRICULUM VITAE 201
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PhD Dissertation
Abstract
The construction industry is the largest consumer of materials in our society. Approximately 40% of
all materials used are related to this section of the industry. Equivalent is the impact of the sectors
activities to the environment in terms of non-renewable energy sources (grey energy), gas emissions
(mainly CO2), solid waste, etc. With concrete being the most widely used construction material
(second only to water in total volumes consumed annually by society) and cement being the essential
glue in concrete, emphasis should be placed on investigating and enforcing ways, methodologies
and policies, to make cement manufacturing and the construction industry in general a more
environmental friendly sector. At the same time, by considering, at one hand the significant amount of
research and breakthroughs achieved on structural materials and design, as well as the level of
sophistication of the modern European Standards and structural codes, and on the other hand, the
increasing cases of premature deterioration of concrete structures, particular emphasis should also be
placed on safeguarding the service life of reinforced concrete structures (in addition to tackling their
environmental burden).
That is why it is very important to introduce the sustainable way of thinking and the concept of
industrial ecology on the preliminary design stages of a structure, on the material selection process and
on the service life estimation stage, in achieving a robust durable reinforced concrete (RC) structure
(for a given service life) with the minimum environmental burden.
Thus, the main objective of the present Thesis is to focus on identifying and quantifying a
structured framework of the appropriate methodologies in formulating an Integrated Design
Process (IDP) for the design of durable and sustainable structures at the minimum
environmental and economical cost (without compromising issues of structural safety) and also
in identifying and demonstrating ways of industrial ecology for the sustainable development of
the cement and construction industry.
A significant step forward for a thorough durability design process of reinforced concrete structures is
the development of software packages, based on predictive models, for the estimation of concrete
strength and service life. Such an attempt, in full compliance with the European Standards for cement
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J.G. Tapali
and concrete, is presented in Chapter 2. Upon defining the concrete mix design, the software
calculates the main chemical and volumetric characteristics, as well as the compressive strength, of
concrete. By taking into account the environmental conditions where the structure will be exposed,
concrete service life is predicted, using fundamental mathematical models (based on reaction
engineering principles) that simulate the reinforced concrete deterioration mechanisms leading to
corrosion of the embedded reinforcement (caused by either carbonation or chloride ingress). A
validation process of the yielded results is also presented, and the effectiveness of the simulation tool
in designing for durability is illustrated. The goal of this study is to promote wider acceptance in
achieving feasible and durable solutions to structural concrete design problems.
Considering the well known environmental issues of cement manufacturing (direct and indirect levels
of CO2 emissions), clinker replacement by supplementary cementing materials (SCM) can be a very
promising first step in reducing considerably the associated emissions. However, such a reduction is
possible up to a particular level of SCM utilization, influenced by the rate of its pozzolanic reaction. In
Chapter 3, a (4-step) structured methodology is proposed in order to be able to further adjust the
concrete mix design of a particular SCM, in achieving additional reduction of the associated levels of
CO2 emissions and being at the same time accepted from a derived concrete strength and service life
point of view. On this note, the aim of this study is twofold. To evaluate the environmental
contribution of each concrete component and to provide the best possible mix design configuration,
balanced between the principles of sustainability (low environmental cost) and durability (accepted
concrete strength and service life). It was proved that such a balance can be achieved by utilising SCM
by-products in the concrete mix, reducing in this way the fixed environmental emissions without
compromising the long-term safety and durability of the structure.
Utilization of biomass ash from agro-industrial by-products (containing large amounts of silica in
amorphous form) in cement manufacturing and/or concrete production can be an alternative solution
to the incorporation of the traditionally used supplementary cementing materials (SCM). An
evaluation of biomass ashes, identified in the literature, with varying SiO2 contents in terms of
concrete strength and performance in chloride exposure is the focus of Chapter 4. Results indicate
that these materials are effective on concrete strength development and extremely efficient in reducing
the concrete permeability. The dependency of this behavior on the level of SiO2 of the ash content was
examined in depth and was concluded that it is affected by the composition of other components of the
biomass ash.
Main objective of Chapter 5 is to identify the detailed economical outcome for rice hush ash (RHA)
valorization technique as a pozzolanic material and main biomass ash. A techno-economical analysis
of producing advanced and high-added value material from RHA is presented. The study was
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PhD Dissertation
elaborated in the framework of pilot production in a Greek rice industry. The importance of the issues
examined is further enhanced by the emphasis given nowadays on adaptation of energy and emissions
reducing solutions by the construction industry. Utilization of supplementary cementing materials
(SCM) in concrete design, such as RHA, should be a very promising first step in reducing
considerably the associated materials environmental footprint.
In contrast to common approach that often involves extensive pre-grinding the utilization potential
of RHA as an SCM, in its untreated form was further examined. This is to meet industrys increasing
awareness for lower embodied energy cement and concrete. Given the availability of current raw
materials in cement manufacturing, what is needed is to be able to achieve an optimum approach,
between sustainability and durability when designing concrete structures. Under this frame, as-
produced RHAs (D50 of approx. 70 microns) were examined with respect to their inherent
characteristics and their impact on the performance of cement-based mortars. Strength, hydration and
durability properties were considered. Untreated RHA exhibits moderate pozzolanicity and a low
efficiency factor of approximately 0.5-0.6. Its very high chemical reactivity (active silica ratio of
approx. 90%) cannot be exploited since the lack of adequate specific surface slows down its
engagement in hydration reactions. Taking into consideration their untreated nature, it can be
supported that they exhibit an acceptable strength potential after 28 days, complying even
marginally with the strength class (42.5) of the used cement. Durability results revealed that there is
no need to pre-treat RHA in order to achieve equal or even better performance than mortar with plain
cement in terms of sorptivity (50% increase for 15% RHA usage) and resistivity. Untreated RHA
however fails as most SCMs do to improve carbonation resistance since for a 15% cement
replacement, carbonation depth was almost doubled. Overall, results indicate that usage of untreated
RHA in cement-based systems is an alternative to decrease their carbon profile, as long as cement
replacement is kept relatively low (below 15%).
The internationally acclaimed efforts to reduce man-made CO2 emissions require a more rigorous
approach to be adopted by the construction industry. Given the need to provide a durable solution that
guarantees a minimum service life, on a common reinforced concrete structure, the issue of sustainable
durability design is of paramount importance. Bearing in mind that the major source of emission of
gasses in concrete manufacturing arise from the clinker production process, during cement
manufacturing several means of reducing the environmental footprint have been suggested, as
incorporation of cement replacement materials. The present Thesis contributes to the evaluation of the
environmental cost of each component of concrete and to provide the best possible mix design
configuration (by means of a holistic analytical software tool) in terms of low environmental cost, as
well as, to assess this proposed configuration in terms of strength and durability requirements. Overall,
it has to be emphasized that through the present Thesis a new indicator is proposed for design
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J.G. Tapali
purposes: the environmental cost, which can be added to the existing strength, durability and
economic cost indicators towards an integrated design optimization of concrete structures. Finally, the
incorporation of new SCM, as biomass ashes and especially RHA, offers new perspectives for
decreasing the environmental cost of constructions.
Keywords: biomass ash, cement; concrete; durability; environmental cost; optimization; predictive
models; rice husk ash; service life; supplementary cementing materials; sustainability.
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PhD Dissertation
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16
PhD Dissertation

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17
J.G. Tapali
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18
Chapter 1 - PhD Dissertation
Chapter 1. Introduction
1.1 Brief description of the building sector
The building sector stands worldwide a prior position in generic industrial/technological activities. It
is considered to be the largest industry in European grounds, with an annual turnover of 1.5 trillion
that corresponds to 11% of total European income and employs almost 20% of total work force of EU
(European Commission 2013). Equivalent is the impact of the sectors activities to the environment in
terms of non-renewable energy sources (grey energy), gas emissions (mainly CO2), solid waste etc.
The leading position in the building sector is held by cement/concrete industry (65% work force, 80%
gas emissions, European Commission 2013). The following three subjects are matters of great
significance for the construction industry:
The immense need for structure for rapid urbanization of our current civilization.
The necessity for balance among industrial development and environment.
The crisis in the space of durability of constructions and especially concrete.
Construction in Europe (construction market forecasting network EUROCONSTRUCT 2013)

performs still unfavourable in 2013. The decline of total construction output results from various
factors:
- dislocations because of the public debt crises,
- the pressure to save on public households and
- uncertainty about the future economic development.
The pressure on European construction will lead to a lower output in 2013 which is expected to
decrease by 2.8% compared to the previous year. This is the result of the leading construction market
forecasting network EUROCONSTRUCT, which includes 19 European countries, see Fig. 1.1.
Austerity measures are mainly dampening civil engineering, while the weak overall economy along
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J.G. Tapali
with high unemployment and a lack of consumer confidence dampens the prospects for housing and
non-residential construction.
Figure 1.1 Construction activity and economic growth in Europe (EC-19) at 2012 prices (source:
75th EUROCONSTRUCT Conference - Copenhagen, 2013).
The European public debt crisis dampens the outlook mainly in civil engineering. This sector has
been shrinking continuously for four years. It declined by one fifth compared to 2009 (when it was
supported by budgetary stimulus measures). Extensions and renovation of infrastructure projects were
delayed which led to overloads in some areas. Public bodies especially in northern and central Europe
are aware of this and are planning to react - therefore increasing investments and growth in civil
engineering are expected in 2014.
The European economic recovery is being delayed despite the improving international framework and
increasing economic activity in the United States and the emerging countries. The outlook for private
consumption, labor and income are therefore dampened. Unemployment is expected to reach its
maximum in 2013. These factors are influencing building construction negatively. Non-residential
construction, especially commercial building and office construction are especially under pressure. All
in all construction output in building is expected to shrink by -3.3%. The declines in Greece, Spain and
Portugal are most severe.
European housing market was also negatively affected by the poor economic performance. In 2013
about 1.3 million housing units will be completed within the 19 Euroconstruct countries about
125,000 units less than in 2012. Banks tightened their credit volume but also the demand for loans is
20
decreasing, despite the low interest rate. However, since the beginning of 2013 there are some signs of
improvement. In UK for instance due to appropriate governmental policies, the housing industry is
moving up with more new buyers around and house loans available from the banks.
On the other hand, the renovation market is performing more stable. On the one hand side
investment volumes in renovation are lower so the project risks are smaller than in new construction
on the other hand many European countries provide public funds which help stimulating the sector.
Figure 1.2 Forecast for concrete consumption up to 2100 (WBCSD 2009).
Consumption of cement is closely linked to both the state of economic development in any given
country or region and to the economic cycle. In mature markets, such as in Europe, where cement
consumption per capita still varies considerably from one country to another, cement sales are
dependent on evolution and habits in the construction sector, a sector that is itself following very
closely (usually after a brief delay) the evolution of the economy in general. Even though the global
economic recession which began in 2008 led to a notable slowdown in construction activity, signs of
stabilisation in the EU construction industry after a two-year drop are already appearing and an
increase in construction spending and cement sales is expected. It is predicted that global demand for
cement is expected to rise 4.1% yearly through 2013, to 3.5 billion metric tons in 2013, valued at $246
billion. Overall at the rate of cement consumption before the effects of the economical crisis and based
on the early signs of improvement, the demand for concrete (hence of cement) is expected (Fig. 1.2) to
rise to about 18 billion tonnes a year by 2050 (WBCSD 2009).
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J.G. Tapali
In 2010, the economic recession in Greece had a negative impact on both private and public
construction activity. In terms of production, the increase in prices of solid and liquid fuels, as well as
the higher cost of electricity, was added to the cost of cement production. This trend was
counterbalanced in part by the use of alternative fuels, such as the combustion of dried sludge from
biological sewage processing, tires, and other materials. Almost all capital expenditure from Greek
Cement manufacturers in 2010 was related to investments in emissions reduction, such as use of
alternative fuels.
1.2 Environmental impacts of the building sector
The construction sector and cement industry, in particular, plays a major role in meeting society's
needs for housing and infrastructure that are expected to increase considerably in the developing
world. The challenge we face is to develop processes and practices that will curb the intensity of CO2
emissions produced in order to strike a balance between climate change risk and global growth.
From a production point of view almost every type of structural material used has a considerable
impact on the local and global environment. In general, any set of construction materials entails
certain aspects of environmental cost (in the form of carbon dioxide and other gasses emissions
and grey energy consumed) from its manufacturing stage to its end-use (fixed environmental cost),
or during-use of the structure (operational environmental cost) according to the particular type of
construction.
In concrete production for example (CEMBUREAU 2009), the main emissions to air are associated
with the cement-making process, where during the stage of clinker formation, CO2 gasses and other
greenhouse emissions are emitted to the atmosphere (0.873 tonnes of CO2 gases are emitted per 1 ton
of cement produced (WBCSD 2005, 2009). Bearing in mind that, cement manufacturing is a mature
industry applying the same chemical process (in principle) for more than a hundred years (thus any
revolutionary breakthroughs are rendered at a slow pace) and by considering that facts that, the
construction sector accounts for a considerable share of the total EU final energy consumption (more
than 42%) and produces more than 35% of all the greenhouse emissions (WBCSD 2009, Zampini
2009), with cement manufacturing contributing 5% of the global man made CO2 emissions, increasing
emphasis should be placed on investigating and enforcing ways, methodologies and policies, to make
cement manufacturing and the construction industry in general a more environmental friendly sector.
The construction activity is a major contributor to environmental pollution and especially to

greenhouse gases emissions (GHG). At world level, civil works and building construction consumes
22
60% of the raw materials extracted from the lithosphere (Bribian et al. 2011). According to data from
the Worldwatch Institute, the construction of buildings annually consumes 40% of the stone, sand and
gravel, 25% of the timber and 16% of the water in the world (Arena and Rosa 2003). Buildings
through their construction, use and demolition, consume approximately 50% of the final energy
consumption in the members states of the European Union and contribute almost 50% of the CO2
emissions released in the atmosphere (Dimoudi and Tombra 2008). As referred, the Portland cement
manufacturing industry represents 5-7% of the total CO2 anthropogenic emissions (Hendricks et al.
2004, Humphreys and Mahasenan 2002). The manufacture, transport and installation in a building
made of materials such as steel, concrete and glass require a large quantity of energy, despite them
representing a minimal part of the ultimate cost in the building as a whole. This contradiction is known
as the Rule of the Notary (Bribian et al. 2011).
Concrete is second only to water in total volume produced and consumed annually by society. The fact
that concrete has very good mechanical and durability properties explains why it has become the most
important building material. Nevertheless, concrete has an enormous environmental footprint (Meyer
2008). First of all production of concrete each year creates a major need for natural resources. The
production of Portland cement is energy intensive and is also responsible for CO2 emissions. The
cement subsector consumes approximately 1215% of the total industrial energy use. Therefore, this
subsector releases CO2 emissions to the atmosphere as a result of burning fossil fuels to produce
energy needed for the cement manufacturing process. Moreover, the concrete industry requires large
water consumption. Construction and demolition waste have a high environmental impact as well.
However, many aspects of the environmental cost in construction have not been analyzed yet. The
concrete industry faces a great challenge which is the sustainable design of buildings and structures by
taking into account environmental and financial factors. The competition among constructors imposes
the application of green technology in the production process and the marketing of new and more
durable building materials. Therefore, since environmental issues have become really important,
construction industry must adjust to the principles of sustainable development. The implementation of
specific environmental policies and the adoption of proper methods by industries can result in the
reduction of CO2 emissions from reinforced concrete constructions.
1.2.1 Environmental cost components
The main environmental impacts of construction activity are: air pollution, waste pollution, noise
pollution and water pollution. More specifically, the most harmful environmental effects of materials
and energy consumption due to construction are:
global warming
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J.G. Tapali
acid rain
resource depletion
habitat destruction by fuel extraction
environmental damage from processing and transportation photochemical smog
At the Kyoto Conference in December 1997, developed countries agreed to cut their emissions of
greenhouse gases by an average of 5.2% in the period 2008 to 2012.The target for the European Union
was an 8% reduction, shared out amongst Member States. According to the definition in the Kyoto
Protocol to the United Nations Framework Convention on Climate Change (UNFCCC), GHG
(Greenhouse Gas) includes six types of gas, namely carbon dioxide (CO2), methane (CH4), nitrous
oxide (N2O), hydroflurocarbons (HFCs), perfluorocarbons (PFCs) and sulphur hexafluoride (SF6).
Figure 1.3 System boundary of GHG emissions in the construction of buildings (Yan et al. 2010).
Fig.1.3 defines the system boundary of greenhouse gas emissions in building. Processes embraced in
construction of buildings are: production of building materials (including acquisition of raw materials
and manufacture of building materials), transportation of building materials to construction sites and
erection of buildings (including disposal of waste and auxiliary materials incurred in the construction
work). Energy consumption in these processes accounts for GHG emissions (Yan et al. 2010).
The main sources of GHG emissions in building construction therefore are:

a) Manufacture and transportation of building materials
embodied GHG emissions of building materials, which are GHG emissions due to
energy consumption for manufacture of building materials before transporting to
construction sites
24
GHG emissions from transportation for building materials, which are GHG emissions
due to fuel and energy consumption for transporting building materials to construction
sites
b) Energy consumption of construction equipment

GHG emissions from fuel combustion of construction equipment
GHG emissions due to electricity used for construction equipment
c) Energy consumption for processing resources

emissions due to electricity used for processing fresh water and sewage
d) Disposal of construction waste

GHG emissions from fuel combustion of transportation for construction waste
The main way to estimate the environmental cost of construction is by measuring the emissions
of CO2 during the production, transport and use of materials in construction. In addition, the
calculation of energy consumed by industries contributes to the estimation of environmental cost of
construction. This energy (kWh) is responsible for CO2 emissions to the environment. In addition,
other factors like the consumption of raw materials, noise pollution, emissions of other gases or dust
are counted in the total environmental cost.
There are many research studies about the environmental cost of buildings and constructions in
general. The results of these studies are very interesting and must be taken into consideration, since
they provide useful information. For example, it was found that all the life cycle phases cause serious
environmental impacts, but operational phase has the highest percentage of energy consumption and
emissions (80-85% of total energy consumption and emissions) in a buildings life (Zampini 2009,
Penttala 1997, Flower and Sanjayan 2007, Gerilla et al. 2007). Furthermore, commercial buildings
were found to have a higher environmental footprint, compared to the residential buildings. All these
issues need of course further investigation and analysis.
The construction industry must adopt the principles of sustainable development in order to reduce its
environmental footprint. Sustainability means meeting the needs of today without compromising the
ability of future generations to meet their needs. Sustainable Construction aims to apply this
principle to the construction industry by providing ways of buildings that use less virgin
material and less energy, cause less pollution and less waste but still provide the benefits that
construction projects have brought us throughout history. A typical Sustainable Construction
Project involves the following criteria in the phases of Design, Construction and Use (Table 1.1).
25
J.G. Tapali
Table 1.1 Criteria for a sustainable construction project.
DESIGN CONSTRUCTION USE

Integrated Design Environmental Policy Extended Design life
Sustainable Materials Insulation Waste Reduction Targets Building Log Books
Utility Conservation Commission Systems
Fitting Specifications Materials Purchase Audits Native plant species
HVAC Systems (Heating, Materials Waste Audits Recycling facilities
Ventilating, and Air Conditioning)
White Goods Site Recycling HVAC Services
Water Systems Ecological Conservation Modular Maintenance
Lighting Performance reporting Internal Environment
1.2.2 Environmental impact of building materials
The main building materials used in constructions are: Concrete (cement, aggregates, water, additives,
admixtures), steel, bricks, wood, glass, mortars and other materials. The fact that concrete has very
good mechanical and durability properties explains why it has become the most important building
material. It is mouldable, adaptable, relatively fire resistant, generally available and affordable.
Nevertheless, concrete has an enormous environmental footprint. First of all its production each year
creates a major need for natural resources. The production of Portland cement is energy intensive and
is also responsible for CO2 emissions. Moreover, the concrete industry requires large water
consumption while construction and demolition waste have a high environmental impact as well.
Cement accounts for two-thirds of total energy use in the production of non-metallic minerals. In
terms of CO2 emissions, cement production is by far the most important activity in this category.
Global cement production grew from 594 Mt in 1970 to 2,284 Mt in 2005, with the vast majority of
the growth occurring in developing countries, especially China. The production of cement clinker
from limestone and chalk is the main energy consuming process in this industry. The most widely
used cement type is Portland cement, which contains 95% cement clinker. Clinker is produced by
heating limestone to temperatures above 950 C. Cement production is an energy-intensive process in
which energy represents 20 to 40% of total production costs. Most of the energy used is in the form of
fuel for the production of cement clinker and electricity for grinding the raw materials and finished
cement. Since cement production consumes on average between 4 to 5 GJ per ton of cement, this
industry uses 8 to 10 EJ of energy annually.
26
The electricity use in cement production varies between 90 and 150 kWh per ton. According to the
GNR database, in the year 2006, the global average electricity consumption was 111 kWh per ton of
cement. The electricity consumption of 90% of the 844 cement plants covered in the database are
between 89 and 130 kWh/t. Significant variations exist between countries and regions. According to
the IEA (IEA, 2007), electricity consumptions ranges from 90 to 120 kWh/t of cement, except for the
United States, Mexico and Canada where typical figures are all above 120 kWh/t of cement. Grinding
may account for a significant part of electricity consumption (up to 100 kWh/t) In a dry process, the
electricity consumption share is 38% for cement grinding, 24% for raw material grinding, 22% for
clinker production including grinding of solid fuels, 6% for raw material homogenisation, 5% raw
material extraction and blending, and 5% for conveying, packing and loading.
There are two very different sources of carbon dioxide emissions during cement production.
Combustion of fossil fuels to operate the rotary kiln is the largest source: approximately tons of CO2
per ton of cement. But the chemical process of calcining limestone into lime in the cement kiln also
produces CO2: CaCO3 CaO + CO2. This chemical process is responsible for roughly ton of
CO2 per ton of cement. Although, the main CO2 emissions from concrete production are associated
with cement manufacturing, other concrete constituents entail environmental loads, see Table 1.2. The
CO2 emissions from concrete production are the summation of the emissions from the chemical
conversion process in clinker production (during cement manufacturing), from the energy
consumption due to fossil fuel combustion (also during cement manufacturing), from the electrical
energy required for the grinding of any additive materials and from the energy required (in terms of
fuel consumption) for the transportation of the raw materials and of the final product (Penttala 1997,
Flower and Sanjayan 2007).
Table 1.2 CO2 emissions from cement and concrete production (Penttala 1997, Flower and Sanjayan
2007).
lbs CO2 per ton of lbs CO2 per cu. yd. of Percent of total
cement concrete CO2 (%)
CO2 emissions from energy 1,410 381 60
use
CO2 emissions from calcining 997 250 40
of limestone
Total CO2 emissions 2,410 631 100
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J.G. Tapali
Figure 1.4 Energy consumption from production of building materials (EC DG Env. 2004).
Fig. 1.4 allows a comparative analysis of the energy that is consumed for the production of different
building materials.
Fig. 1.5 and 1.6 are based on a life cycle assessment of building materials (Bribian et al. 2011). These
figures show the relative contribution of some building materials to the primary energy demand and
CO2 emissions associated with a square meter in a Spanish standard block of flats. It is obvious that
the most popular materials such as steel, cement and ceramics have a high impact.
Figure 1.5 Contribution of primary energy demand for the manufacture of the materials needed in
the construction of 1 m2 gross floor area (Bribian et al. 2011).
28
Figure 1.6 Contribution of CO2 emissions associated with the manufacture of the materials needed in
the construction of 1 m2 gross floor area (Bribian et al. 2011).
Fig. 1.7 shows the CO2 emissions for wooden and SRC (Steel Reinforced Concrete) type of
construction, according to each life cycle stage (Gerilla et al. 2007). The carbon emissions in the
operation stage have the highest rate compared to the other stages.
Figure 1.7 Environmental impacts of the calculated emissions (Gerilla et al. 2007).
Fig. 1.8 shows the environmental impacts of housing. The most serious environmental impact of
building is Global Warming Potential because the highest air pollutants are from carbon emissions.
SRC houses have a higher environmental footprint compared to the wooden type of construction
(Gerilla et al. 2007).
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J.G. Tapali
Figure 1.8 Total life cycle carbon emissions for each life cycle stage (Gerilla et al. 2007).
1.2.3 Reduction of the environmental cost
Decreasing the environmental cost is a matter of importance, thus a lot of measures are proposed such
as restriction of residue production and emission responsible for the greenhouse phenomenon,
extended use of industrial by- products and their various mixtures, more efficient use of mineral and
metallic sources, increased use of recycled materials in conjunction with lengthening of the
construction durability. In order to achieve a balance between sustainability and durability, as far as
concrete design is concerned incorporation of supplementary cementing by products, such as silica
fume and fly ash, has been suggested (Tapali et al. 2013).
According to Meyer (2009) the potential tools and strategies to meet the environmental challenges
are:
1. To replace as much Portland cement as possible by supplementary cementitious materials

(SCM), especially those that are by-products of industrial processes, such as fly ash, ground
granulated blast furnace slag and silica fume, etc.
2. To use recycled materials in place of natural resources.
3. To improve durability and service life of structures, thereby reducing the amount materials
needed for their replacement.
4. To improve concretes mechanical and other properties, which can also reduce the amount of
materials needed.
5. To reuse wash water.
30
What follows is a brief report of the main methods and materials which can be used by concrete
industry.
Fly ash
Fly ash is an important pozzolan with cementitious properties, which has a lot of advantages compared
with regular Portland cement. The heat of hydration is lower, which means that fly ash can be used as
a cement substitute for mass structures. Moreover, fly ash is a byproduct of coal combustion, which
otherwise would be a waste product. It also improves the strength and durability properties of concrete
and costs less than Portland cement.
The relatively slow rate of strength development of fly ash concrete is a disadvantage where high early
strength is required (Papadakis 1999b, Papadakis 2000a). Another critical issue is the need for quality
control since the sources of coal are different in power plants. So, the physical and chemical properties
of fly ash can vary to a significant extend.
High Volume Fly Ash Concrete (HVFA) is constituted by the following minimum mix criteria:
a minimum of 50% fly ash,
a low water content (130 kg/m3),
less than 200 kg/m3 cement content, and
a low water-cementicious ratio (less than 0.4).
Ground granulated blast furnace slag (GGBFS)
GGBFS is a by- product of the steel industry which also has cementitious properties. It is the glassy
granular material formed when molten blast- furnace slag is rapidly chilled, as by immersion in water
(ACI Committee 233, 1995). GGBFS has a positive effect on many mechanical and durability
properties of concrete and generates less heat of hydration.
Silica fume
Condensed silica fume is a by-product of the semiconductor industry which can improve the strength
and durability of concrete. It has a lot of benefits both as a pozollan and a filler material, so it is now
produced specifically for the concrete industry (Papadakis 1999a).
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J.G. Tapali
Recycled concrete
Because of the large amount of fines found in recycled concrete there are technical problems
incorporating recycled concrete aggregates into new concrete. Recycled concrete aggregates (RCA)
have generally lower densities than the original material used, because of the cement mortar that
remains attached to the aggregate particles (De Pauw 1981). This fact is also the reason why there is
larger water absorption of RCA in comparison with virgin aggregates. Moreover, as a result of the
demolition of existing structures, there are a lot of contaminants in recycled concrete like plaster, soil,
wood, gypsum, asphalt and rubber which can degrade the strength or durability of the concrete. RCA
also causes a reduction in elastic modulus, an increase in creep and shrinkage deformations, as well as
high permeability of concrete, whish decreases its durability (Meyer 2009). Another matter of concern
is the fact that there is a large variability in quality of RCA obtained from different sources which may
lead to significant variations in strength of concrete with RCA from different sources.
Post-consumer glass
Post- consumer glass can also be used as aggregate for concrete. Glass has many advantages such as
zero water absorption, high hardness, good abrasion resistance, excellent durability, chemical
resistance and aesthetic potential.
Other materials
There are also many other and especially new by- products that can be used as substitutes for
conventional ingredients of concrete. For example various biomass ashes with pozzolanic properties
can replace Portland cement. Rice husk ash (RHA) which is the residue from burning rice husk at rice
industries can also be excellent for use in cement and concrete production.
1.2.4 Towards a sustainable construction
The implementation of environmental management in construction activities has a lot of benefits for
the community and the contractors. EMS is an environmental management system defined in the
standard ISO 14000 which can improve the environmental performance in construction, including or
suggesting various environmental management measures such as:
Legal requirements on environmental protection

Reduction, reuse and recycling of construction and demolition wastes
Imposing responsibilities of protecting environment on managerial staff
32
Applying environmentally friendly technology

Providing in- house training on environmental management
Establishing waste management plan
Continuous efforts in improving environmental management
Inclusion of environmental management in tendering requirements
Effective communication on environmental issue between all layers of
subcontractors
Close supervision at site level
There are many factors that can affect the environmental impact of a building, such as the choice of
structural solutions and building materials. Furthermore, the length of the buildings service life has an
influence on the environmental assessment of a building. Numerous environmental assessment tools
have been developed to allow scientists analyze the environmental performance of buildings.
Since decreasing the environmental cost is a matter of importance, a lot of measures are proposed such
as restriction of residue production and emission responsible for the greenhouse phenomenon,
extended use of industrial by- products and their various mixtures, more efficient use of mineral and
metallic sources, increased use of recycled materials in conjunction with lengthening of the
construction durability. Several different studies IEA (2008, 2009), CSI (2009), ECRA (2009), CCAP
(2008), McKinsey (2008) have focused on potential cement industry emissions reduction.
Generally, there are four main levels concerning the reduction of carbon emissions:
1. Thermal and electric efficiency

2. Use of alternative fuels- use of less carbon-intensive fossil fuels and more alternative (fossil)
fuels and biomass fuels in the cement production process
3. Clinker substitution by supplementary cementing materials (SCM)
4. Carbon capture and storage (CCS) capturing CO2 before it is released into the atmosphere
and storing it securely so it is not released in the future (Cement Technology Roadmap 2009).
Considerable amount of work on developing analytical models for the evaluation of SCM in concrete
using the concept of efficiency factors (or k-values, to compare the relative performance of
supplementary cementing materials on concrete strength and durability) by Papadakis and Tsimas
(2002) and preliminary work undertaken by Antiohos et al. (2013) on identifying and evaluating new
promising industrial by products have identified the high-added value of incinerated residues from
industrial by-products on cement and mortar. The k-factor, defined as the part of the SCM, which can
be considered as portland cement, providing to the SCM-concrete equal property values with the
33
J.G. Tapali
concrete without SCM, will allow the estimation of the relative value of these materials comparing to
cement, an important factor of the mix design process for the preparation of the building product.
Coal; 23,90%
Lignite;
5,70%
Fuel oil;
4,20%
Gas; 0,90%
Petcoke;
Waste fuels;
48,60%
16,70%
Figure 1.9 Fuel consumption in the EU-25 (EC DG Env. 2004).
In terms of fossil fuels, solid fuels such as coal (23.9%), petroleum coke (48.6%) and lignite are
traditionally used (Fig. 1.9) in the burning process in clinker kilns (and to a lesser extent, natural gas
and fuel oil). However, further waste and by-products with recoverable calorific value can be used as
fuels in a cement kiln, replacing a portion of conventional fossil fuels, if they meet strict specifications
(being 20-25% less carbon intensive than traditional coal and petcoke). In this way recycling wastes
from one process as raw materials and fuels for another creates a web of relationships between
industries that moves society closer to a zero-waste economy. Co-processing of these types of
materials in the cement industry prevents equivalent CO2 emissions at waste incineration disposal
installations, plus any mineral content in alternative fossil fuels that is incorporated into the clinker
matrix during its formation, thus there is no residual ash and associated heavy metal disposal, such as
is typically found in incinerators.
In general, the use of waste as an alternative energy source varies widely across regions, influenced
by the level of development of waste legislation, law enforcement, waste collection infrastructure and
local environmental awareness. In Europe, where up to 70% of clinker production installations source
energy from alternative fuels, 45% of installations source a small portion of energy from biomass, in
contrast to Latin America, where 30% of energy used is derived from biomass. Overall, there is
significant potential to further develop the sourcing of thermal energy from alternative fossil fuel,
especially waste, and biomass across all regions of the world.
34
Figure 1.10 Waste materials utilised by TITAN Cement Company (TITAN, 2010).
Currently in Greece, TITAN Cement Company (Fig. 1.10) utilises 1.4% biomass derived energy in the
cement manufacturing process (the largest source of thermal energy, 98.6% calorific basis, comes
from conventional energy sources). Efforts however are being made to increase this percentage. An
alternative fuel system that fires biomass (from sawdust flour, wood chips) to both the calciner and
main burner was recently commissioned by TITAN in Roanoke cement plant in Virginia, USA. The
goal of the project was to reduce the amount of coal consumed by the plant. The initial results have
shown that the materials introduced through the calciner show great promise towards the ultimate goal
of reducing coal consumption while at the same time not affecting clinker quality or increasing
emissions. Furthermore, a considerable number of research projects initiated by TITAN provide
additional efforts to address the current climate change challenges of the cement manufacturing
process, by focusing on: the sustainability of both product and production process (ECOSERVE), on
utilization of agricultural wastes in the cement industry (LABELAGRIWASTE), on the utilization of
mineral industry by-products as raw materials for cement production (PERLITE REJECTS
UTILIZATION), on the utilization of an aluminum industry by-product as raw material for the raw
mix of clinker production (RED MUD FOR CLINKER) and on delivering roads constructed with
minimal CO2 burden, utilizing alternative raw materials and hydraulic binders with minimum clinker
content (TEFRODOS Project). Further to the above, the fluctuation (increased at the moment) in
prices of solid and liquid fuels, as well as the higher cost of electricity, in cement production leads the
cement manufacturing companies to investigate and invest in the use of alternative fuels.
Considering all of the above, and bearing in mind that industrial ecology is The Science of
Sustainability through minimising consumption of natural resources and production of waste with
optimal utilization of raw materials in order to produce products with optimal performance and life
expectancy, there is a wide sector that needs to be infiltrated by eco-cement and other relative
sustainable products and techniques.
35
J.G. Tapali
Utilisation of industrial by-products as cement replacement materials and as alternatives to fossil fuels
will reduce the amount of the associated CO2 emissions from both burning of fuel and the clinker
calcination process, considerably. As fuel-related CO2 emissions are about 40% of total emissions
from cement manufacture, the CO2 reduction potential from alternative fuel use can be significant. It
has been estimated that utilisation of alternative fuels (to a certain percentage) can be 20-25% less
carbon intensive than coal. Utilisation of 15,500 tons of sewage sludge in one of the coordinators
cement plants, reduced the requirements for fossil fuels by about 5,000 tons, while lowering by about
18,000 tons the plants CO2 emissions.
By utilising the industrial by-products proposed in this thesis as cement replacing materials, rice husk
for example, components of strength equal to a reference mixture can be obtained. At the same time, a
similar durability in general is achieved, plus significant ecological benefits, due to industrial by-
products use (reduction of pollution from incinerated residues of rice husk arbitrary disposal) and
decrease in the cement quantity (energy saving and CO2-emission reduction). As the k-value for
treated residues of rice husk is estimated around 1 (equal to Portland cement), it means that this
material can substitute equally cement, and by taking into account that 1 t of cement production emits
1 t CO2, every 1 t of RHA used in building applications almost save 1 t of CO2 emissions.
Figure 1.11 Consumption of raw materials and % of alternative raw materials used in clinker and
cement production by TITAN Cement Company (TITAN, 2010).
36
In 2010, 21.3 million tons (dry basis) of raw materials were used by TITAN for cement production, in
which approximately 5.3% of all raw materials (about 1.1 million tons dry basis) were alternative raw
materials, namely by-products and waste disposals from other industries, such as fly ash, pyrite ash,
blast furnace slag and industrial gypsum (Fig. 1.11). Overall the utilisation of the previously
mentioned percentages of alternative materials resulted on 697.7 kg/t of cement direct CO2 emissions.
The aim is to increase the utilisation of alternative materials as cement replacements to 12% and
combined with the utilisation rate of alternatives to fossil fuels previously mentioned, achieve an
overall value of direct CO2 emissions in the range of 628 kg/t of cement, by 2015.
1.3 Objectives and structure of the present thesis
1.3.1 Objectives of the present thesis
The present thesis targets on formulating in a structured way every process contributing on an
optimization stage between the principles of sustainability, durability and economical aspects and on
introducing new industrial by-products, easier to obtain throughout Europe and with less energy
requirements for their processing than the ones currently used, in cement manufacturing (as clinker
replacement materials), or as concrete additions, enforcing in this way an industrial ecology scheme,
in achieving less greenhouse gas emissions from cement manufacturing.
Through the formulation and utilisation of an Integrated Design Process (IDP) tool, the concept of
minimizing greenhouse gas emissions, will be incorporated at the initial preliminary design stages of a
reinforced concrete structure, at the materials selection stage, where by:
- estimating the overall fixed environmental cost of materials

- the operational environmental cost of the structure
- its economical aspects
- and the fulfilment of service life estimation for concrete deterioration,
the optimum balance among the previous will be estimated, in determining the best overall
configuration for the design of a durable RC structure, at the minimum environmental and
economical cost.
Overall the aim is to define the necessary structures of an analytical framework (IDP) and demonstrate
its outputs (optimised process, suggestions for sustainable development, eco-concrete) in order to
37
J.G. Tapali
introduce into everyday construction practice the principles of industrial ecology and enhancement of
durability of structures, in achieving a considerable decrease of the associated CO2 emissions.
The principal objective of this thesis is to provide an integrated approach of the environmental impacts
in concrete industry by enhancing an innovative software tool (EUCON, Papadakis and Efstathiou
2005). The guidelines outlined herein would be very helpful for the engineers and the companies,
whereas the manufactures would be encouraged to promote green concrete and sustainable
methods of building.
A great challenge nowadays is the construction of durable concrete structures which are friendly to the
environment and live longer. The basic conclusions that arise from this particular presentation must
affect, apart from the scientific community, all other social and political groups, since the
environmental problems caused by constructions have become really worrying.
The principles of Sustainable Development and Green buildings have dominated in recent years. The
concrete industry in particular leaves an enormous environmental footprint; therefore the situation
must be improved, as soon as possible. The use of supplementary cementing materials is suggested, in
order to achieve a balance between sustainability and durability. Governments should give financial
and legislative incentives to manufactures and industries and urge them to apply new methods and a
more sustainable and green technology. Furthermore, construction organizations must improve their
environmental performance by using environmental management systems (EMS). Life Cycle Analysis
can contribute in the reduction of environmental impacts across the entire life cycle of materials, from
production to disposal.
The technology (Fig. 1.12) for the development and production of eco-cement consists of the
utilization of industrial by-products as cement replacement materials, (hence reducing clinker, which
contributes to a large extent on greenhouse gas emissions) and of the incorporation of alternative fuels
from the agro-industrial sector as rachis/pedicels from wine production, olive leaves and pruning from
the olive/olive oil industry and biomass, to produce thermal energy for its manufacture. More
specifically, specially treated (to a certain level of fineness) incinerated residues of industrial by-
products, from the rice and paper making industries, with a high efficiency factor (an index of their
pozzolanic activity, crucial in establishing cementitious properties) can be fed to the process, with the
other typically used raw materials in cement manufacturing.
In order to achieve a balance between sustainability and durability in concrete design incorporation
of supplementary cementing byproducts, such as biomass ashes and more specifically rice husk ash
(RHA) are examined. On the utilisation of rice husk ash, results from a National Research project
38
(PYRICE 2008) indicated that the specially physicochemical treated RHA, given its high specific
surface and great amount of silica soluble in alkaline conditions, can be converted into advanced and
high-added value cementitious materials, improving significantly the concrete strength and durability
and decreasing the constructions environmental cost due to use of less cement and/or the extension of
its lifetime. Considering the fact that approximately 600 million tonnes of rice paddy is produced on
an annual basis and that on average 20% of the rice paddy is husk, and that production of paper sludge
is estimated to be in the region of 1 million tonnes annually just in the UK, vast quantities of these
incinerated residues are available and easy to obtain. At present, in Greece, most RHA quantities
remain unexploited leaving significant space for successful applications towards a greener cement or
concrete production.
Alternative Fuels Biomass,

agro-industrial by-products
Rice Husk Ash Paper Sludge
Figure 1.12 Schematic process of cement manufacture and ways for a greener production.
1.3.2 Innovative aspects of the thesis
Based on the previously stated arguments on defining the objectives and the environmental problem
tackled in this thesis, its main aim can be defined as, to focus on identifying and quantifying a
structured framework of the appropriate methodologies in formulating an Integrated Design
Process (IDP) for the design of durable and sustainable structures at the minimum possible
environmental and economical cost (without compromising issues of structural safety) and also in
identifying and demonstrating ways (through the use of various biomass ashes) of industrial ecology
for the sustainable development of the cement and construction industry.
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J.G. Tapali
For such a structured and comprehensive framework of processes as the IDP, counterbalancing issues
of sustainability with durability and economical cost has yet to by developed. Analytical tools
currently available cover, either the spectrum of environmental and economical constraints through
life-cycle analysis, as the SUSCON (2008), GEMIS (Fritsche 2008), or SimaPro (Goedkoop et al.
2010) tools (not easy to follow by the key players involved in the field of the construction sector), or
the service life estimation of concrete structures, as the DURACON (2006), Conclife (Bentz et al.
2001), Life-365 (Ehlen et al. 2009) tools and EUCON (Papadakis and Efstathiou 2009) which in
addition to the service life and strength estimation incorporated economical aspects on the design
procedure.
There is yet a certain tool to be developed offering a holistic approach and an accurate prediction of
the service life of the structure, under harmful exposure conditions, with the minimum environmental
and economical impact. Such is the purpose of the IDP tool (see Chapter 3).
Having said that, and bearing in mind the environmental burden of the cement manufacturing process
(due to the clinker calcination process) several research solutions have been attempted.
Innovative new types of clinker have been produced (or are being developed at the moment), as the
types of Novacem (Ruffolo et al. 2010), a carbon-negative cement based on magnesium silicates
(rather than limestone as the Ordinary Portland Cement), Calix (Sweeny and Sceats 2009) produced in
a reactor by rapid calcination of dolomitic rock in superheated steam, Calera (Bren 2011) based on a
mixture of calcium and magnesium carbonates and hydroxides and finally the type of clinker currently
being developed by the AETHER Life+ project (Walenta and Morin 2011).
In addition, efforts have been made in providing methodologies on recycling schemes of solid and
liquid wastes from the production process of cement manufacturing, in cold climates (Betongindustri
2001) and in the Mediterranean Region (ECO-SERVE 2004).
The only restriction of the above mentioned types of research efforts is that they have to be accepted
by the cement manufacturing companies, as their enormous (indeed) benefits on the reduction of the
associated emissions it is estimated to be fully validated in a time frame of 5-10 years from today
(Mehta and Monteiro 2006).
What is actually currently being utilized is incorporation of cement replacement materials (replacing
clinker to a certain percentage). It has been shown, that incorporation of fly ash, silica fume or ground
granulated blast furnace ash, besides the effect they entail on early concrete strength and volume
stability (Papadakis and Tsimas 2002, 2005), they improve to a great extend the overall environmental
40
contribution (Papadakis and Tsimas 2003). It has been calculated that 18% replacement of Portland
cement results in a 17% reduction of the CO2 emissions (Mehta and Monteiro 2006, Ecosmart
Concrete 2008, WBCSD 2005, 2009).
Bearing all of the above in mind, it becomes prudent to identify and investigate new forms of
materials, effective to be used as cement replacement, and easier to obtain on a European but also on a
local level and also without having considerable energy requirements for their processing.
Industrial by-products, from the rice and paper making companies (or from the agro-industrial sector
as rachis/pedicels from wine production, olive leaves from the olive/olive oil industry) can potentially
be used as partial cement replacement materials. Rice husk ash (RHA), an agricultural waste material,
produced by controlled burning of rice husk, or paper sludge ash, produced from the incineration at
800 C of paper mill sludge, have shown to contain reactive silica and alumina (in the form of
metakaolin) as well as lime (CaO) which could contribute chemically to the Portland cement
ingredients. At present, in Greece, most RHA remains unexploited and is disposed as waste, resulting
in a potential environmental threat and a factor of soil and atmosphere pollution.
It is believed that the approach presented in this thesis, although simple in principle, is currently
missing and that it will provide considerable benefits in tackling the environmental burden of the
construction sector and in providing:
A structured framework of analytical methodologies, as an Integrated Design Tool, in evaluating in a

balanced (optimized) way every aspect on material selection for the design of a RC structure
(environmental cost, durability and service life, economical cost)
A new type of cement with reduced clinker content, or concrete incorporating simple in principle, but
innovative in results, new types of pure industrial by-products (hence enhancing the principle of
industrial ecology), easily accessible in the majority of the European Countries.
1.3.3 Structure of the thesis
According to the above introduction and analysis of the thesis objectives, the structure of the thesis
has as follows:
Chapter 1: Introduction. First, a brief description of the building sector is presented in terms of
basic characteristics, production rates, and relevance with the economy growth. The
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J.G. Tapali
various environmental impacts of the building sector are then analysed and grouped,
whereas the potential measures, products and techniques for reducing the environmental
cost of the constructions are outlined. Then, the objectives and structure of the present
thesis are given.
Chapter 2: Durability and sustainability of concrete constructions. Service life and durability of
concrete are strongly related with the environmental footprint of constructions. It is
obvious that a structure with a longer service life is less harmful to the environment
during the phase of operation. In this chapter, therefore the concrete durability according
to the European Standard EN 206 is first presented, then, the development of a concrete
mix design is given including the concrete constituents and, finally, the concrete service
life estimation tool (EUCON) is presented with the improvements made in the present
work on environmental cost assessment.
Chapter 3: Environmental cost of concrete production Estimation & optimization. First, the
concept of the environmental cost is analysed and then it is estimated for the concrete
production according to literature and industry data. A structured methodology for
concrete mix design optimization (Integrated Design Process) is then presented in
details and utilized for typical applications offering a significant tool towards
sustainable concrete constructions.
Chapter 4: Investigation on the effectiveness of biomass ashes as pozzolanic materials. The main
aim is to shed light on the specific influence of the main characteristics of biomass ashes
on concrete strength development and performance in chloride exposure, exploring in
this way their future utilization in cement and concrete manufacturing. Types and
evaluation methodology for biomass ashes are presented together with results and
discussion on their evaluation as concrete constituents.
Chapter 5: Utilization of rice husk ash in the building sector Technoeconomical analysis and
environmental benefits. Focusing on rice husk ash - a main biomass ash and efficient
pozzolanic material, provided its amorphous and fine state techno-economical aspects
are analyzed in detail. A technical and financial study and a preliminary design for the
industrial production of the RHA-derivatives for building applications, including an
environmental analysis, are performed. The limitations that may arise are examined,
such as the registration of these new materials according to EU and national regulations.
Knowing the above components, the rate of return on investment is estimated and the
42
first conclusions for the undertaking of this investment are drawn, offering as well high
environmental benefits to the construction industry.
Chapter 6: Conclusions. The main conclusions drawn from all thesis chapters are presented and the
corresponding suggestions for engineers, manufacturers, practitioners and all interesting
parties are given as well.
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J.G. Tapali
44
Chapter 2. Durability & sustainability of concrete

constructions
2.1 Introduction
Concrete is the most widely used building material. Its good performance in service, including
durability, is the second important characteristic after the usual required mechanical properties.
However, during the last decades the problems of unsatisfactory durability of structures, especially
reinforced concrete ones, are in a dramatic increase. This causes not only economic impacts, because
the repairing expenses of deteriorated structures are almost equal to the cost of construction of new
ones, but also industrial, environmental and social problems due to decrease of reliability and safety
(see Fig. 2.1). Service life and durability are strongly related with the environmental footprint of
constructions. It is obvious that a structure with a longer service life is less harmful to the
environment during the phase of operation.
initial (good quality)

Performance
initial (medium quality)

repair
minimum acceptable limit

Service lifetime
Time
Figure 2.1 Relationship between concrete performance and service life (Papadakis 2005).
45
J.G. Tapali
The type and rate of degradation processes for concrete and reinforcement determines the resistance
and the rigidity of the materials, the sections and the elements making up the structure. This reflects in
the safety, the serviceability and the appearance of a structure, i.e., determines the performance of the
structure. Concrete working life or service lifetime is the period of time during which the
performance of the concrete structure will be kept at a level compatible with the fulfilment of the
performance requirements of the structure, provided it is properly maintained. As observed in Fig. 2.1,
this service life may be achieved either due to initial good quality, or due to repeated repair of a not so
good structure. The modeling of the deterioration mechanisms and the quantitative approach of the
service life is the main objective of the present chapter.
As durability of a structure is called the ability to resist against environmental attacks without its
performance to drop below a minimum acceptable limit. Three following main factors define the
concrete durability: the initial mix design (quality and relevant quantity of the concrete constituents),
structure design, construction and maintenance, and the specific environmental conditions.
Deterioration of building materials in service is every loss of performance, and it may be the result of
a variety of mechanical, physical, chemical or biological processes. Concrete (and cement products in
general) is also susceptible to all these types of deterioration (CEB 1989, Mehta 1997, Neville 1995,
Illston and Domone 2001, Richardson 2002). The final result of these mechanisms is mainly cracking.
Cracking will occur whenever the tensile strain to which concrete is subjected exceeds the tensile
strain capacity of the concrete.
As mechanical processes causing cracking can be considered the direct loading and the imposed
deformations:
Cracking caused by direct loading is the result of normal load effects (i.e., bending, shear,
tension, etc.) applied to sections.
As imposed deformations causing cracking can be considered differential settlement of
foundations, earthquakes and other natural catastrophes.
A mechanical process causing deterioration of the surface is the erosion either by abrasion or
cavitation.
Concrete cracking due to the reinforcement corrosion (and creation of internal expansion tensions)
will be included in the chemical processes, because these are responsible for the corrosion.
As physical processes causing cracking can be considered the plastic shrinkage, the plastic settlement,
the temperature differences, the shrinkage, and the frost action:
46
Plastic shrinkage is caused by capillary tension in pore water when the water loss by
vaporization exceeds the supply by bleeding water (mainly map surface cracking).
If settlement of concrete is hampered by the reinforcement or by the formwork, cracking can,
also, occur (longitudinal cracks).
One of the major causes of cracking is movement resulting from the cooling of members from
the temperatures generated by hydration of cement during a specific use of concrete.
Shrinkage is the load independent, long-term deformation of concrete because of its decrease
in volume due to drying.
In the case of water freezing in concrete, the following physical processes are of major
importance: Transition from water to ice involves an increase in volume by 9% and the
freezing point is depressed as the pore diameter decreases. In the case of completely water-
filled pores such expansion will cause splitting of concrete. Owing to this fact, a sufficient
quantity of pores not filled with water shall be available.
The chemical processes causing concrete deterioration can be divided into two categories according to
the medium they influence: concrete or reinforcement:
The first category includes the chemical attack of aggressive substances (ions and molecules) on
concrete. A precondition for chemical reactions to take place within the concrete is the presence of
water in some form (liquid, vapor). In general, the reactions between the aggressive substance (present
in the concrete or transported from the environment) and the reactive substance of the concrete take
place as they meet each other. However, often because of the low rate of transport of these substances,
these reactions may take many years to show their detrimental effect. For practice, the most important
chemical attacks on concrete are the acid, the sulphate and the alkali attack:
The action of acids (as well ammonium salts, magnesium salts, and soft water) on the
hardened concrete is practically a conversion of all the calcium compounds to the calcium
salts of the attacking acid. These salts are very soluble and can be removed by dissolution or
abrasion destroying the binding capacity of the cement.
Sulphate attack on concrete is the reaction of sulphate ions with the aluminate phase of the
cement, which causes expansion of the concrete, leading to cracking and disintegration.
In the case of the alkali attack, alkalis from the cement present in the pore solution can react
with silica containing aggregates resulting in the formation of alkali-silica gel (alkali-
aggregate reaction). This may lead to destructive expansion if enough water is present, starting
with small surface cracks and followed eventually by complete disintegration.
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J.G. Tapali
Reinforcing bars in concrete are protected from corrosion by a thin oxide layer that is formed on their
surface due to high alkalinity, i.e., the high pH-value, of the surrounding concrete. Corrosion may start
when this protective layer is destroyed:
either by chloride penetration (and the chloride content exceeds a critical value),
or due to a reduction in the pH value of concrete to values below 9. Such a reduction in
alkalinity is the result of carbonation of the Ca(OH)2 in the concrete mass, i.e., of its reaction
with the atmospheric CO2 that diffuses through the concrete pores.
In marine or coastal environments, and when deicing salts come in contact with the concrete surface,
chloride penetration is the main mechanism that paves the way to initiation of reinforcement
corrosion. In all other cases, and especially in CO2-rich urban and industrial areas, carbonation of
concrete is the main mechanism leading to steel corrosion. Furthermore, the two mechanisms are
synergetic, i.e., chloride action is accelerated by carbonation. However, corrosion of the reinforcement
is possible, if sufficient moisture and oxygen are available.
Finally, many biological processes, such as growth on concrete structures may lead to mechanical
deterioration caused by lichen, moss, algae and roots of plants:
Microgrowth may cause chemical attacks by developing humic acid, which dissolves the
cement paste.
In practice, the most important type of biological attack occurs in sewer systems, where
hydrogen sulfide (formed during anaerobic conditions) may be oxidized by bacteriological
action to form sulfuric acid, thus resulting in an acid attack on concrete.
Fig. 2.2 summarises various possible causes of concrete deterioration and gives some indication of the
age at which the various forms of cracking can be expected to occur.
Nowadays, an issue of importance is the durability design of reinforced concrete structures with a
minimum service life of at least 50 years. However, a great number of concrete structures especially in
coastal and urban areas begin to deteriorate in 20 to 30 years or even less time. This fact has serious
economic impacts, as the repair of structures demands large financial amounts. Freyermuth (2001) has
emphasized on these matters and suggested a service life time of 100 to 120 years for future structures.
For the assessment of durability two basic indicators are used: in order to evaluate the carbonation
exposure, carbon dioxide penetration front is calculated, while for chloride ingress, the adequate
concrete cover needed to sustain that ingress for a period of also 50 years is estimated.
48
direct
MECHANICAL loading
imposed
deformations
plastic
shrinkage
plastic
settlement
PHYSICAL temperature
differences
shrinkage
frost
early action late
acid, sulfate, alkali
CHEMICAL attack
reinforcement
corrosion
micro-
BIOLOGICAL growth
H2S
attack
HOUR DAY WEEK MONTH YEAR CENTURY
Figure 2.2 Deterioration mechanisms and possible time of appearance of cracking or damage
(Papadakis 2005).
During the past years, a lot of experimental work has been conducted in this scientific field since
durability is considered as one of the most serious issues that concern engineers all over the world.
Nowadays, there is an increasing awareness of the durability problems that appear in many concrete
structures. In spite of significant advances made in concrete technology in recent years, the problems
of unsatisfactory durability of structures are still among the serious issues concerning the international
community of engineers today. Corrosion of steel reinforcement is the most serious durability problem
of reinforced concrete structures. It impairs not only the appearance of the structure, but also its
strength and safety, due to the reduction in the cross-sectional area of the reinforcement, the
deterioration of bond with the surrounding concrete, and the significant reduction of the steel ductility
properties (Richardson 2002, Apostolopoulos and Papadakis 2008, Apostolopoulos et al. 2013).
Over the past decades, an enormous amount of energy has been expended in laboratory and field
studies on concrete durability. The results of this research are still either scattered widely in the journal
literature or mentioned briefly in popular textbooks; having although partially been included in the
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J.G. Tapali
relevant industry consensus documents as well as in the relevant codes for construction. Moreover, the
theoretical approaches of deterioration mechanisms with a predictive character are limited to some
complicated mathematical models not widely applicable in practice. A significant step forward could
be the development of appropriate software for computer estimation, including reliable mathematical
models and strengthened by adequate supporting experimental data. Durability design should get as
much attention as structural design since it has to quantify the anticipated functional lifespan. There is
opportunity for both simulation computer-aided modelling as well as full-scale engineering
corroboration both in the laboratory and in the field.
In the present Chapter, the basis of the development of a computer estimation of the concrete service
life is presented. After the definition of concrete mix design and structure characteristics, as well as the
consideration regarding the environmental conditions where the structure will be found, the concrete
service life can be reliably predicted using fundamental mathematical models that simulate the
deterioration mechanisms. The prediction is focused on the basic deterioration phenomena of
reinforced concrete, such as carbonation and chloride penetration. Basic principles of chemical and
material engineering are applied to simulate the physicochemical processes, yielding simple and
accurate mathematical models for design and prediction. Aspects on concrete strength and the
production cost are also considered. Field observations and data collection from existing structures are
compared with predictions of service life using the above model. A first attempt to develop a database
of service lives of different types of reinforced concrete structure exposed to varying environments is
finally included. The work approach presented herein is in full compliance with the European
Standards; for cement: EN 197 and concrete: EN 206; however, after a short modification it can be
applied to any other standard.
On the European Standard for concrete, EN 206 durability is approached by the definition of limiting
parameters on cement and concrete composition (water-to-cement ratio, cement content, etc.), as well
as by the development of performance-related methods (PRMs). Such a method (PRM) is necessary
when a service life significantly higher of 50 years is required, or when the environmental actions are
particularly aggressive. A PRM considers each relevant deterioration mechanism, in addition to the
service life of the structure, and the criteria which define the end of this service life, in a quantitative
way. It can be based on data derived from established performance test methods for each relevant
mechanism, or on the use of proven predictive models. Considering that in reinforced concrete the
most serious deterioration mechanisms are those leading to reinforcement corrosion, it is therefore
necessary, if a long service life is required, the modeling attempts to focus on these types of
mechanisms/chemical attack processes. Bearing all of the above in mind, a significant step forward
could be the development of appropriate software for the estimation of concrete service life, using
reliable mathematical proven models, based on performance-related methods.
50
In this chapter, a deterministic simulation tool in full compliance with the European Standards for
cement and concrete, based on proven predictive models developed by Papadakis et al, for estimation
of concrete service life and strength is briefly presented. Emphasis is given on the concept of service
life estimation and on tool validation and utilisation schemes. Based on this software tool (EUCON),
an environmental assessment of the concrete production is performed and use is possible offering
significant input for a life cycle analysis.
2.2 Concrete durability and the EN 206 approach
The European Standard EN 206 specifies requirements for the constituent materials of concrete, the
properties of fresh and hardened concrete and their verification, the limitations for concrete
composition, the specification of concrete, the delivery of fresh concrete, the production control
procedure, the conformity criteria, and evaluation of conformity. It defines tasks for the specifier,
producer, and user. During its development, consideration was given to detailing a performance-
related approach to the specification of durability, but it was concluded that test methods to specify
durability are not yet sufficiently developed to include them in the standard. However, this standard
permits the continuation and development of performance-related methods for assessing durability, as
does the present chapter.
According to EN 206, environmental actions are those chemical and physical actions to which the
concrete is exposed and that result in effects on the concrete or reinforcement or embedded metal that
are not considered as loads in structural design. The main deterioration actions considered are
corrosion of reinforcement induced either by carbonation or chlorides, cyclic freezing and thawing,
and chemical attack. The environmental actions are classified in exposure classes; their selection
depends on the provisions valid where concrete will be used. Durability is then specified either
through the traditional practice of limiting values of concrete composition (more widely used) or by
performance-related methods. The requirements shall take into account the intended service life of the
concrete structure.
2.2.1 Limiting values for concrete composition
In the absence of European standards for absolute performance testing of concrete, requirements for
the method of specification to resist environmental actions are given in EN 206 in terms of established
concrete properties and limiting values for concrete composition. The requirements for each exposure
class shall be specified in terms of permitted types and classes of constituent materials, maximum
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J.G. Tapali
water-cement ratio, minimum cement content, minimum concrete compressive strength class
(optional), and, if relevant, minimum air-content of the concrete.
Due to lack of experience on how the classification of the environmental actions on concrete reflect
local differences in the same nominal exposure class, the specific values of these requirements for the
applicable exposure classes are given in the provisions valid in the place of use. A recommendation
for the choice of limiting values for concrete composition and properties is given in Annex F
(informative) of EN 206. These values are based on the assumption of an intended service life of the
structure of 50 years, and refer to the use of cement type CEM I conforming to EN 197.
2.2.2 Performance-related design methods
The requirements related to exposure classes may be established by using performance-related

methods for durability and may be specified in terms of performance-related parameters, e.g., scaling
of concrete in a freeze/thaw test. Guidance on the use of an alternative performance-related design
method with respect to durability is given in Annex J (informative) of EN 206. The application of an
alternative method depends on the provisions valid in the place of use of the concrete.
The performance-related method considers each relevant deterioration mechanism, the service life of
the element or structure, and the criteria which define the end of this service life, in a quantitative way.
Such a method may be based on satisfactory experience with local practices in local environments, on
data from an established performance test method for the relevant mechanism, or on the use of proven
predictive models.
A general guidance and some applications are given:
Some aggressive actions are best dealt with a prescriptive approach, e.g., alkali-silica reaction,
sulphate attack, or abrasion.
Performance-related design methods are more relevant to corrosion resistance and possibly,
freeze-thaw resistance of concrete. This approach may be appropriate where:
- a service life significantly differing from 50 years is required;

- the structure is special requiring a lower probability failure;
- the environmental actions are particularly aggressive, or are well defined;
- standards of workmanship are expected to be high;
- a management and maintenance strategy is to be introduced, perhaps with planned
upgrading;
52
- significant populations or similar structures, or elements, are to be built;

- new or different constituent materials are to be used;
- method based on limiting values for concrete composition has been used in design, but there
has been a failure to conform.
In practice, the level of durability achieved depends on a combination of design, materials, and
execution.
The sensitivity of the design concept, the structural system, the shape of members and structural/
architectural detailing are all significant design parameters for all methods of durability design.
Compatibility of materials, the construction method, the quality of workmanship, levels of control
and quality assurance are significant parameters for all methods of durability design.
The required durability performance depends on the required service life, on the possible future
use of the structure, on the particular protective measures, on the planned maintenance in service,
and on the consequences of failure, in the particular local environment.
For any required level of performance, it is possible to derive alternative equivalent solutions
from different combinations of design, material and construction factors.
The level of knowledge of the ambient and local micro-climate is important in establishing the
reliability of performance-related design methods.
The performance-related methods that may be used include:
The refinement of the method of limiting values for concrete composition, based on long-term
experience of local materials and practices, and on detailed knowledge of the local environment.
Methods based on approved and proven tests that are representative of actual conditions and have
approved performance criteria.
Methods based on analytical models that have been calibrated against test data representative of
actual conditions in practice.
The orientation of the present work included in this chapter is towards the development of
performance-related methods based on predictive models that have been calibrated against test data
representative of actual conditions in practice.
First, however, basic information on concrete mix design as well on physicochemical characteristics of
concrete constituents will be given.
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J.G. Tapali
2.3 Concrete mix design
2.3.1 Constituent materials for concrete composition
Concrete is the material formed by mixing cement, aggregates and water, with or without the
incorporation of admixtures and additions, which develops its properties by hydration of the cement.
The general concept for concrete mix design as presented herein is in full compliance with the most
spread existing standards for concrete production, such as the European Standard for concrete: EN
206. For the present application, a concrete volume is assumed that contains certain amounts of
cement, additions (optional), aggregates, water, and admixtures (optional) only, see Fig. 2.3. To the
above materials entrained or entrapped air should be added.
All these materials have to comply with the corresponding standards for the constituent materials, for
instance in the case of European Standards: EN 197 (Cement), EN 450 (Fly ash for concrete), EN
13263 (Silica fume for concrete), EN 12620 (Aggregates for concrete), EN 1008 (Mixing water for
concrete), EN 934-2 (Admixtures for concrete), etc.
CONCRETE :
Cement: main constituents: portland clinker, blast furnace slag, silica fume, pozzolanic
materials (natural or natural calcined pozzolanas), fly ash (siliceous or calcareous),
burnt shale, and limestone
minor additional constituents: all main constituents except clinker
calcium sulphate, additives
+
Additions: type I (filler aggregate, pigments), type II (fly ash, silica fume)
+
Aggregates: fine, coarse
+
Water: mixing water
+
Admixtures: retarder, accelerator, air-entraining, plasticizer, superplasticizer, etc.
+
Air: entrained, entrapped
Figure 2.3 Constituent materials for concrete composition (European Standard EN 206-1, 2000).
54
a. Cement
Cement is a hydraulic binder, i.e. a finely ground inorganic material which, when mixed with water,
forms a paste that sets and hardens by means of hydration reactions and processes and which, after
hardening, retains its strength and stability even under water. General suitability for concrete
production is established for cement conforming to EN 197-1. Cement conforming to this European
Standard, termed CEM cement, shall, when appropriately batched and mixed with aggregate and
water, be capable of producing concrete or mortar which retains its workability for a sufficient time
and shall after defined periods attain specified strength levels and also possesses long-term volume
stability.
Hydraulic hardening of CEM cement is primarily due to the hydration of calcium silicates but other
chemical compounds may also participate in the hardening process, e.g., aluminates. The sum of the
proportions of reactive calcium oxide (CaO) and reactive silicon dioxide (SiO2) in CEM cement shall
be at least 50% by mass when proportions are determined in accordance with EN 196. CEM cements
consist of different materials that are statistically homogeneous in composition resulting from quality
assured production and material handling processes. According to this standard, a cement may
comprise of main constituents, minor additional constituents, calcium sulphate and additives, see
Table 2.1.
A main constituent is a specially selected inorganic material in a proportion exceeding 5% by mass

related to the sum of all main and minor additional constituents. As main constituents the following
are used: portland cement clinker, blast furnace slag, silica fume, pozzolanic materials (natural or
natural calcined pozzolanas), fly ashes (siliceous or calcareous), burnt shale, and limestone. Portland
cement clinker is the main constituent that all cement types contain (CEM I to CEM V). It is made by
sintering a precisely specified mixture of raw materials (raw mill, paste or slurry) containing elements,
usually expressed as oxides, CaO, SiO2, Al2O3, Fe2O3 and small quantities of other materials. It is a
hydraulic material which shall consist of at least 2/3 by mass of calcium silicates (3CaO. SiO2 and
2CaO. SiO2), the remainder consisting of aluminium and iron containing clinker phases and other
compounds. The ratio by mass CaO/SiO2 shall be not less than 2.0. The content of magnesium oxide
(MgO) shall not exceed 5.0% by mass.
All other main constituents (except clinker), defined only in the present work as supplementary
cementing materials (SCM), may be divided into natural materials and artificial ones. To the former
natural pozzolanic materials and limestone belong. To the second category granulated blast furnace
slag, silica fume, calcined pozzolanas, fly ashes, and burnt shale belong. In EN 197 these materials are
defined as follows:
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J.G. Tapali
Table 2.1 Types of common cements according to European Standard EN 197-1*.
Main Nota- Main constituents** Minor

types tion addit.
K S D P Q V W T L/LL const.
PORTLAND CEMENTS
CEM I I 95-100 - - - - - - - - 0-5
PORTLAND-COMPOSITE CEMENTS
II/A-S 80-94 6-20 - - - - - - - 0-5
II/B-S 65-79 21-35 - - - - - - - 0-5
II/A-D 90-94 - 6-10 - - - - - - 0-5
II/A-P 80-94 - - 6-20 - - - - - 0-5
II/B-P 65-79 - - 21-35 - - - - - 0-5
II/A-Q 80-94 - - - 6-20 - - - - 0-5
II/B-Q 65-79 - - - 21-35 - - - - 0-5
CEM II/A-V 80-94 - - - - 6-20 - - - 0-5
II II/B-V 65-79 - - - - 21-35 - - - 0-5
II/A- 80-94 - - - - - 6-20 - - 0-5
W 65-79 - - - - - 21-35 - - 0-5
II/B-W
II/A-T 80-94 - - - - - - 6-20 - 0-5
II/B-T 65-79 - - - - - - 21-35 - 0-5
II/A-L 80-94 - - - - - - - 6-20 0-5
II/B-L 65-79 - - - - - - - 21-35 0-5
II/A-M 80-94 6-20 0-5
II/B-M 65-79 21-35 0-5
BLASTFURNACE CEMENTS
III/A 35-64 36-65 - - - - - - - 0-5
CEM III/B 20-34 66-80 - - - - - - - 0-5
III III/C 5-19 81-95 - - - - - - - 0-5
POZZOLANIC CEMENTS
IV/A 65-89 - 11-35 - - 0-5
CEM IV/B 45-64 - 36-55 - - 0-5
IV
COMPOSITE CEMENTS
V/A 40-64 18-30 - 18-30 - - - 0-5
CEM V V/B 20-38 31-50 - 31-50 - - - 0-5
* The composition is expressed as % by mass of the main and minor additional constituents.
** Notation exclusively for the present table: portland clinker (K), blast furnace slag (S), silica fume (D), pozzolana (natural,
P or natural calcined, Q), various fly ashes (siliceous, V or calcareous, W), burnt shale (T), and limestone (L or LL).
56
Granulated blast furnace slag is made by rapid cooling of a slag melt of suitable composition, as
obtained by smelting iron ore in a blast furnace slag and contains at least 2/3 by mass of glassy slag
and possesses hydraulic properties when suitably activated. It shall consist of at least 2/3 of the sum of
(CaO+MgO+SiO2), the remainder contains Al2O3 together with small amounts of other compounds.
The ratio by mass of (CaO+MgO)/(SiO2) shall exceed 1.0.
Silica fume originates from the reduction of high purity quartz with coal in electric arc furnaces in the
production of silicon or ferrosilicon alloys and consists of very fine spherical particles containing at
least 85% by mass amorphous SiO2.
In EN 197, pozzolanic materials are defined as the natural substances of siliceous or silico-aluminous
composition or a combination thereof (in general, however, pozzolanic materials are also fly ash and
silica fume). Pozzolanic materials do not harden in themselves when mixed with water but, when
finely ground and in the presence of water, they react at normal ambient temperature with dissolved
calcium hydroxide, Ca(OH)2, to form strength-developing calcium silicate and calcium aluminate
compounds. These compounds are similar to those which are formed in the hardening of hydraulic
materials. They consist essentially of reactive SiO2 (>25.0 % by mass) and Al2O3, the remainder
contains Fe2O3 and other oxides. These materials may be natural pozzolanas (materials of volcanic
origin or sedimentary rocks) or natural calcined pozzolanas (materials of volcanic origin, clays, shales
or sedimentary rocks, activated by thermal treatment).
Fly ash is the combustion residue (coal mineral impurities) in coal-burning electric power plants,
which flies out with the flue gas stream and is removed by electrostatic or mechanical precipitation.
Ash obtained by other methods shall not be used in cement that conforms the EN 197-1. Fly ash may
be siliceous or calcareous in nature. The former has pozzolanic properties; the latter may have, in
addition, hydraulic properties. Siliceous fly ash is a fine powder of mostly spherical particles having
pozzolanic properties. It consists essentially of reactive SiO2 and Al2O3, the remainder contains Fe2O3
and other compounds. The proportion of reactive CaO shall be less than 10.0% by mass and the
content of free CaO shall not exceed 1.0% by mass. The reactive SiO2 content shall not be less than
25.0% by mass. Calcareous fly ash is a fine powder having hydraulic and/or pozzolanic properties. It
consists essentially of reactive CaO, reactive SiO2 and Al2O3, the remainder contains Fe2O3 and other
compounds. The proportion of reactive CaO shall not be less than 10.0% by mass and the content of
free CaO shall not exceed 1.0% by mass. The reactive SiO2 content shall not be less than 25.0% by
mass, if the reactive CaO is between 10-15% by mass; if the reactive CaO is greater than 15% by mass
certain strength levels should be required.
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Burnt shale, specifically burnt oil shale, is produced in a special kiln at temperatures of approximately
800 oC. Owing to the composition of the natural material and the production process, burnt shale
contains clinker phases, mainly dicalcium silicate and monocalcium silicate. It also contains, besides
small amounts of free calcium oxides and calcium sulphate, larger proportions of pozzolanically
reacting oxides, especially SiO2. Consequently, in a finely ground state burnt shale shows pronounced
hydraulic properties like Portland cement and in addition pozzolanic properties.
Limestone shall meet the following requirements: The CaCO3 content shall be at least 75% by mass,
the clay content shall not exceed 1.20% by mass, and the total organic carbon content shall conform to
one of the following criteria, LL: shall not exceed 0.20% by mass, L: shall not exceed 0.50% by mass
In general, but not accepted in EN 197, to the above SCM may be added slags from metallurgical
furnaces producing steel, copper, nickel and lead, bottom ashes, ashes from incinerators and waste
treatment sludge, metakaolin, red mud from alumina production, etc. These materials may, in some
future revised edition of the standards, be included as cement constituents. However, either
experimentally or at industrial scale all the above additions are extensively used the recent years
especially as ingredients in blended cements and at a lower degree as separately batched constituents
in concrete. Almost only silica fume and siliceous fly ash are used as separately additions in concrete
(see below: concrete additions). However, for all these materials, whatever is their origin in concrete,
besides the effect on usual structural properties, such as strength and volume stability, the concrete
durability should seriously be considered.
A minor additional constituent (mac) is a specially selected inorganic material used in a proportion
not exceeding 5% by mass related to the sum of all main and minor additional constituents. As minor
additional constituents can be used inorganic natural materials, inorganic mineral materials derived
from the clinker production process or main constituents as specified earlier unless they are included
as main constituents in the cement. Inert materials, such as limestone and dust derived from the clinker
production process (materials known as fillers) are usually used. Thus, mac affects only the physical
properties of concrete, such as workability and water retention. However, they shall not increase the
water demand of the concrete appreciably, impair the resistance to deterioration or reduce the
corrosion protection of the reinforcement.
Calcium sulphate (between 3 % and usually 5% by weight of cement) in the form of gypsum or
anhydrite is added to the above constituents to control the clinker flash setting.
58
Various additives may also be added (up to 1% by weight of cement) to improve either the cement
production or cement properties. They shall not promote the corrosion of the reinforcement or impair
the properties of cement, mortar or concrete.
Regarding durability requirements it is stated that, in many applications, particularly in severe

environmental conditions, the choice of cement has an influence on the durability of concrete, mortar
and grouts, e.g., frost resistance, chemical resistance and protection of the reinforcement. The choice
of cement, particularly as regards type and strength class for different applications and exposure
classes shall follow the appropriate standards and/or regulations for concrete or mortar valid in the
place of use.
b. Additions
Addition is a finely divided material used in concrete in order to improve certain properties or to
achieve special properties. The EN 206 deals with two types of inorganic additions:
- nearly inert additions (type I)

- pozzolanic or latent hydraulic additions (type II)
General suitability as type I addition is established for filler aggregate conforming to EN 12620 and
pigments conforming to EN 12878. General suitability as type II addition is established for fly ash
conforming to EN 450 and silica fume conforming to EN 13263. However, EN 206 notes that certain
constituents no conforming to some European Standard may be used in concrete; the establishment of
suitability may result from: a European Technical Approval, or a relevant national standard or
provisions. In general, type II additions may by all the above called supplementary cementing
materials (SCM).
c. Aggregates
Aggregate is a granular mineral material suitable for use in concrete. Aggregates may be natural
(natural collected or just natural, and natural crushed), artificial or recycled from material previously
used in construction. General suitability is established for:
- normal and heavy-weight aggregates conforming to EN 12620. Normal-weight aggregate has

an oven-dry particle density between 2000 3000 kg/m3, when determined according to EN
1097-6. Heavy-weight aggregate has an oven-dry particle density 3000 kg/m3, when
determined according to EN 1097-6.
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J.G. Tapali
- light-weight aggregates conforming to EN 13055-1. Light-weight aggregate of mineral origin

has an oven-dry particle density 2000 kg/m3 when determined according to EN 1097-6 or a
loose oven-dry bulk density 1200 kg/m3 when determined according to EN 1097-3.
Aggregate type, grading and categories, e.g., flakiness, freeze/thaw resistance, abrasion resistance,
fines, shall be selected taking into account the execution of the work, the end use of the concrete, the
environmental conditions and any requirements for exposed aggregate. The maximum nominal upper
aggregate size (Dmax) shall be selected taking into account the concrete cover to reinforcement and the
minimum section width. When aggregates contain varieties of silica susceptible to attack by alkalies
(Na2O and K2O originating from cement or other sources) and the concrete is exposed to humid
conditions, actions shall be taken to prevent deleterious alkali silica reaction using procedures of
established suitability.
c. Water
Suitability is established for mixing water and for recycled water from concrete production
conforming to EN 1008. Total water content is the added water plus water already contained in the
aggregates and on the surface of aggregates plus water in the admixtures and in additions used in the
form of a slurry and water resulting from any added ice or steam heating. Effective water content is the
difference between total water present in the fresh concrete and the water absorbed by the aggregates.
d. Admixtures
Admixture is a material (usually organic) added during the mixing process of concrete in small
quantities related to the mass of cement to modify the properties of fresh or hardened concrete.
General suitability is established for admixtures conforming to EN 934-2.
In general, the admixtures for concrete can be divided into:

admixtures modifying set and hardening:
- accelerators
- retarders
admixtures modifying the mix rheology and the air content:
- water-reducing admixtures (superplasticizers, plasticizers)
- water-retaining admixtures
- thickening admixtures
admixtures entraining air into the mixes:
- air-entraining and air-detraining admixtures
60
- gas-forming admixtures
- foam-forming admixtures
admixtures modifying the resistance to physical and chemical actions:
- frost-resisting and anti-freezing admixtures
- water-repelling admixtures
- permeability-reducing admixtures
- corrosion-inhibiting admixtures
- improving resistance to chemical actions
However, the most largely used products are retarders (0.2-0.4% by mass of cement), accelerators
(0.5-6% by mass of cement), air-entraining admixtures (0.05-0.2% by mass of cement), plasticizers
(0.3-0.5% by mass of cementitious materials), and superplasticizers (0.8-1.5% by mass of
cementitious materials). These representative dosages refer to the total solution of admixtures (as
supplied: solids plus solvent water).
The total amount of admixtures, if any, shall not exceed the maximum dosage recommended by the
admixture producer and not exceed 50 g of admixture (as supplied) per kg cement unless the influence
of the higher dosage on the performance and durability is established. If the total quantity of liquid
admixtures exceeds 3 l/m3 of concrete, its water content shall be taken into account when calculating
the water/cement ratio.
e. Entrained or entrapped air
Entrained air are the microscopic air bubbles intentionally incorporated in concrete during mixing,
usually by use of a surface active agent; typically between 10 300 m in diameter and spherical or
nearly so. Entrapped air is voids in concrete which are not purposely entrained.
2.3.2 Design strategy
The concrete mixture composition and the constituent materials for designed or prescribed concrete
shall be chosen to satisfy the requirements specified for fresh and hardened concrete, including
consistence, density, strength, durability, protection of embedded steel against corrosion, taking into
account the production process and the intended method of execution of concrete works. As designed
concrete called the concrete for which the required properties and additional characteristics are
specified to the producer who is responsible for providing a concrete conforming to the required
properties and additional characteristics. As prescribed concrete called the concrete for which the
composition and the constituent materials to be used are specified to the producer who is responsible
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J.G. Tapali
for providing a concrete with the specified composition. Where not detailed in the specification, the
producer shall select types and classes of constituent materials from those with established suitability
for the specified environmental conditions.
In all specifications regarding concrete production, among the main design parameters are the cement
content (C) and the water-to-cement ratio (W/C). Thus, minimum values of cement content and
maximum values of W/C ratio are specified according to the aggressiveness class of the surrounding
environment. Despite the exposure classes, in all cases, the total equivalent cement content should be
taken into account.
After having specified the fresh concrete composition (mix design: cement C, silica fume S, fly ash F
water W, aggregates A, admixtures D, and entrained or entrapped air air) that fulfils the strength
expectations and standard requirements (e.g., minimum C, maximum W/C ratio, etc.), the concrete
durability should be examined. Let us suppose that the designed service life is Z years. Thus, this
specific concrete composition must be examined if it ensures service life greater than the designed
one, as regards the possible deterioration environment in which the concrete will be exposed.
First the case of concrete carbonation, if any, must be taken into account. The concrete cover, c,
must be higher than the expected carbonation depth within the lifetime Z. An accurate prediction of
this carbonation depth can be obtained using the equations presented in the sequence. If an
unacceptable (due to various technical or economic reasons) cover is predicted then either a different
concrete composition (e.g., lower W/C ratio, higher cement content, etc.) or a protective coating
application shall be proposed. Then the calculation must be repeated until satisfaction.
Having specified the concrete composition and cover as above, the case of chloride penetration, if
any, must then be considered. The equations presented in the sequence have to be solved using the
corresponding parameters, in order to predict the chloride profile into the concrete as a function of
time. Using the Cl-profile at the time equal to Z, the minimum concrete cover can be found at which
and onwards the chloride concentration takes lower values than the critical threshold for corrosion. If
an unacceptable cover is predicted then again either a denser concrete composition or a coating
application should be considered and the calculations are repeated.
If any other deterioration mechanism could take place, e.g., a specific chemical attack, it has to be
considered in a similar way. Finally, the cost of concrete production has to be estimated.
For the initially selected concrete composition the most essential properties have been predicted, such
as strength, service life and cost. The specifier can then alter accordingly the concrete composition
62
and/or the protection measures to improve further every desired property. The design parameters that
ensure full protection (the higher concrete cover and the denser concrete composition or the best
protection measures) among them predicted for resistance against carbonation and chloride
penetration, chemical attack, etc., at the lowest cost, must be finally proposed.
2.4 Concrete service life estimation tool
Many software tools have been developed for the estimation of service life and the computation of
environmental cost in the construction sector. The combination of these models with new technologies
can contribute in the establishment of sustainable building. One of these tools, the EUCON software
package, is a complete and comprehensive solution in calculating: (a) concrete mix design, (b)
concrete service life under harsh environmental agents, (c) corrosion prevention measures. EUCON is
a useful tool based on proven predictive models (according to performance-related methods for
assessing durability), developed and validated by Papadakis et al. (2005, 2007, 2012, 2014), well
published and awarded by the American Concrete Institute (ACI), for the estimation of concrete
service life when designing for durability under harsh environments.
As shown in Fig. 2.2, all physical and mechanical mechanisms for concrete deterioration, except direct
loading and imposed deformations, may exhibit their effect on concrete performance during the first
year of the service life. Chemical and biological mechanisms actually start from the beginning;
however, their detrimental results are observed typically long after the first year. In reinforced
concrete, the most serious deterioration mechanisms are those leading to corrosion of the
reinforcement, which occurs after depassivation due to carbon dioxide or chloride ion penetration. It is
therefore necessary, if a long service life is required, that the modelling attempts to address corrosion
initiation mechanisms and chemical/biological attack processes.
Fig. 2.4 shows the logic diagram followed in the software program development (EUCON) for the
estimation of concrete service life. The underlined actions, connected with the environmental cost,
have been developed under the present Thesis. First, the essential parameters that characterize a
concrete composition (mixture proportions) are selected, and this is the main source on which all other
concrete characteristics depend. Thereafter, the main chemical and volumetric characteristics of
concrete are calculated (chemical composition of hydrated cementitious materials, porosity and related
characteristics) and this is also another source to receive more information. Based on the selected
mixture proportions (cement type and strength class, cement content, water-cement ratio, air content,
aggregate type, type and activity of additions, etc.), the compressive strength class of concrete is
estimated.
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J.G. Tapali
CONCRETE MIX DESIGN (according to EN 197, EN 206)

Selection between 27 cement types (EN-197) and of Standard Cement
Cement Type Strength Class. Composition in clinker, other main constituents, minor
constituents, gypsum. Cement density and content
Type I (filler aggregate and/or pigments), Type II (siliceous/calcareous fly
Additions
ash, silica fume), additions density and content
INPUT Type (retarder, accelerator, air-entraining, plasticizer, superplasticizer),
Admixtures
density, solid content, dosage. Total admixture content
Water added, water from admixtures and aggregates, water density and
Water
content
Aggregates Aggregate type, aggregate density, maximum nominal aggregate size
Air Entrapped-air content, entrained-air content, total air content
OUTPUT Aggregate content, fresh concrete density
CHEMICAL & VOLUMETRIC CHARACTERISTICS OF CONCRETE

Oxide analysis of clinker, oxide analysis and activity of other main
Cement Composition,
INPUT constituents of cement, oxide analysis and activity of silica fume
Oxide Analysis
and fly ash
Reaction degree of other main constituents of cement and concrete additions. Contents of
OUTPUT
calcium hydroxide, calcium silicate hydrate, chemically-bound water, porosity
ESTIMATION ESTIMATION OF ESTIMATION OF COST &

OF CONCRETE SERVICE LIFE WITH SERVICE LIFE WITH ENVIRONMENTAL
STRENGTH RESPECT TO RESPECT TO CHLO- ASPECTS
CARBONATION RIDE PENETRATION
INPUT INPUT INPUT INPUT
All of the previous All of the previous, plus All of the previous, plus All of the previous,
environmental conditions environmental conditions plus
Exposure class Exposure class Financial input

Relative humidity, Internal concentration purchase cost of
CO2-content in air of Cl- materials, mixing,
Use of mortar or other External source of Cl- transport. and
coating (type, Cl- concentration at delivery cost
chemical analysis, concrete surface
width) Degree of exposure Environ. input
Relative humidity environmental
Use of corrosion impact from
inhibitors, coatings, materials
etc. production
OUTPUT OUTPUT OUTPUT OUTPUT

Mean compressive corrosion-initiation Adequate concrete Concrete production
strength period, cover needed to sustain cost
Strength Class corrosion-propagation a corrosion free Environmental
Strength ratio 2/28 period, structure, for a given cost
days total service life service life
Strength Development corrosion-initiation
period
TECHNICAL, ENVIRONMENTAL AND ECONOMICAL OPTIMIZATION

Mixture proportions optimization to achieve the specified strength and durability at the lowest cost.
Figure 2.4 Logic tree of software for estimation of concrete service life, strength, economical &
environmental cost (underlined: developed in the present Thesis).
64
For each significant deterioration mechanism, according to the specific environment where the
structure would be found, an appropriate proven predictive model is used. Concrete carbonation and
chloride penetration are the most common causes for reinforcement corrosion onset, and for further
concrete deterioration. The service life of the structure found in these environments, which cause
either carbonation or chloride penetration, is calculated. The degree of deterioration from a possible
chemical attack is also estimated, either as a reduction in the effective concrete section (in the case of
acid or biological attack) or as a reduction in strength of the affected concrete (in the case of sulphate
or alkali attack). Finally, cost and environmental aspects regarding concrete composition are analysed.
Now, for the initially selected concrete composition, the most essential properties have been predicted,
such as strength, service life and cost. The designer can then modify the concrete composition
accordingly to improve further every required property.
Concrete service life is reliably predicted using fundamental mathematical models that simulate the
basic deterioration mechanisms of reinforced concrete (carbonation, chloride penetration). Principles
of chemical and material engineering have been applied to model the physicochemical processes
leading to concrete carbonation, as well as the processes of chloride diffusion in the aqueous phase of
pores, their absorption and binding in the solid phase of concrete and their desorption.
The procedure suggested in order to export the desired results is the following: First, the essential
parameters that characterize a concrete composition (mix design) are selected. Thereafter, the main
chemical and volumetric characteristics of concrete are calculated (chemical composition of hydrated
cementitious materials, porosity and related characteristics).
Based on the selected mixture proportions the compressive strength class of concrete is estimated. For
each significant deterioration mechanism, according to the specific environment where the structure
would be found, an appropriate proven predictive model is used. The service life of the structure in
these environments, which cause either carbonation or chloride penetration, is calculated. Finally, cost
and environmental aspects regarding concrete composition are analyzed. The designer evaluates the
values of predicted properties (strength, service life, cost) and modifies the initially selected concrete
composition, if necessary, in order to improve one or more of these properties.
2.4.1 Modeling for carbonation exposure
In terms of carbonation exposure, a system of non-linear differential equations developed by

Papadakis et al. models in a quantitative way the physicochemical processes leading to concrete
carbonation. These include the diffusion of CO2 in the gas-phase of pores, its dissolution in the
aqueous film of these pores, the dissolution of solid Ca(OH)2 in pore water, its ultimate reaction with
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J.G. Tapali
the dissolved CO2 and the reaction of CO2 with calcium silicate hydrate (CSH). The solution of the set
of differential equations permits the calculation of the carbonation depth xc, at a given time t, as well
as the estimation of the critical time, tcr,carb, required for the carbonation front to reach the
reinforcement located at a distance c (concrete cover to reinforcement), for both Portland and blended
cements, as well as when additions of supplementary cementing materials (SCM) are used separately
in concrete, according to the following equation:
2 De ,CO 2 (CO 2 / 100)t (0.33CH 0.214CSH )c 2

x , tcr , carb (2.1)
c 0.33CH 0.214CSH 2 De,CO 2 (CO2 / 100)
where, CO2 is the CO2-content in the ambient air at the concrete surface (%), CH and CSH are the
contents of calcium hydroxide and calcium-silicate-hydrate in concrete volume (kg/m3),
De,CO2 the effective diffusivity of CO2 in carbonated concrete (m2/s), where in an ambient
relative humidity, RH (%), is calculated as:
3

6 c air 1 RH 1002.2
De ,CO 2 6.1 10 (2.2)
A
1 air
dA
where, c is the porosity of the carbonated concrete, air the volume fraction of entrapped or entrained
air in concrete (m3/m3), A the aggregate content in concrete volume (kg/m3) and dA the
aggregate density (kg/m3).
Once the carbonation front reaches the embedded bar, corrosion can take place with its known
consequences, including concrete cracking. At that point it can be reasonably assumed that major
repair will be necessary. Hence the appearance of generalized cracking may be considered to signal
the end of the service life of the structure (Zcarb). Overall, the time required to crack the concrete cover
can be expressed (see Fig. 2.5) as the time required for the carbonation front to reach the bar (initiation
period of corrosion, tcr,carb, estimated as mentioned above) plus the time necessary for the layer of rust
to build up around the bar and split the cover (corrosion propagation period, tpr,carb). However, in
certain cases the corrosion rate in carbonated concrete at high relative humidity values can be of such
magnitude, that the arrival of the carbonation front at the bar is followed shortly by splitting of the
concrete cover. Therefore the time tcr,carb required for the carbonation front to penetrate the concrete
cover c can be considered with good approximation as a narrow lower bound to the service life of
reinforced concrete.
66
Progress of the Corrosion of

Reinforcement process Critical level of corrosion
causing concrete cracking
tcr,carb
Time
Initiation Period Propagation Period
Figure 2.5 Schematic illustration of initiation and propagation periods of corrosion in a reinforced
concrete element (Papadakis 2005).
If an approximation of the propagation period is required, then a model of the physicochemical

processes of corrosion and cracking has to be applied. However, until now there is no a generally
accepted fundamental model for corrosion propagation of the concrete reinforcement, attributed to the
complex phenomena of corrosion as well to the definition of detectable effects that define the limit of
an acceptable damage, such as the level of cracking.
An alternative approach would be to assume a zero propagation period ensuring at least the lower limit
for service life. However, this assumption is not valid, especially for low relative humidity when the
propagation period is much higher than the initiation period due to lack of moisture. As a general
conclusion from various works (Morinaga 1991, Richardson 2002), the propagation period depends
strongly on relative humidity. For example 70 % RH results in a propagation period almost double of
the initiation period, while for 80 % RH the propagation period is about half of the initiation period
and for 90 % RH, the propagation period is about 1/5 of the initiation period.
2.4.2 Modeling for chloride ingress
In many studies, chloride transport in concrete is modeled using Ficks second law of diffusion,
neglecting the chloride interaction with the solid phase. However, the latter process is very important
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J.G. Tapali
including binding of chlorides by cement hydration products, ionic interaction, lagging motion of
cations and formation of an electrical double layer on the solid surface, etc.
The physicochemical processes of chlorides (Cl-) diffusion in the aqueous phase, their adsorption and
binding in the solid phase of concrete, and their desorption, are described by the non-linear partial
differential Eq. (2.3) (Papadakis et al. 1996, 2000). Solution of Eq. (2.4), allows the calculation of the
Cl- bound in the solid phase [Cl-(s)].
Cl (aq) De,Cl (1 K eq Cl (aq))

2 Cl (aq)
2

K eq Cl (s)sat (1 K eq Cl (aq)) 2
(2.3)
t x 2
Cl

( s)

K eq Cl (aq) Cl
( s)
1 K eq Cl (aq)
sat (2.4)
initial condition: [Cl-(aq)] = [Cl-(aq)]in at t = 0 (initial concentration)

- -
boundary conditions: [Cl (aq)] = [Cl (aq)]0 at x = 0 (concrete surface),
[Cl-(aq)] / x = 0 at x = M (axis of symmetry)
where, x is the distance from the concrete surface (m), t is the time (s), Keq the equilibrium constant
for Cl- binding (m3 of pore volume/kg), [Cl-(s)]sat the saturation concentration of Cl- in the
solid phase (kg/m3 concrete), [Cl-(aq)] the concentration of Cl- in the aqueous phase, De,Cl-
is the intrinsic effective diffusivity of Cl- in concrete (m2/s), calculated as:
2.4 10 10
De ,Cl eff
3. 5 (2.5)
C kPACT W
2

d d
c W
with eff being the effective (for diffusion) concrete porosity (m3 pore volume/m3 concrete), calculated
as:
eff W d W 0.226 10 3 C kPACT (2.6)
where, C cement content (kg cement / m3 of concrete), PACT the active content of each SCM added
either as cement constituent or as concrete addition, having an efficiency factor k, and dc, dw,
cement and water densities, respectively,
68
Furthermore, the solution of Eq. (2.3) allows the calculation of the adequate (minimum) concrete
cover needed in order to sustain a chloride-induced corrosion free structure for a given service life, as
well as the estimation of the time (critical time for chloride-induced corrosion, tcr,chlor) required for the
total chloride concentration surrounding the reinforcement (located at a distance c from surface) to
increase over the threshold for depassivation. Afterwards, the propagation of corrosion process takes
place at a rate that depends strongly on the availability of both oxygen and water. The service lifetime
of a structure, regarding chloride penetration, can be considered to be at least tcr,chlor.
In the case of a reinforced concrete (RC) structure where the concrete cover is not crack-free, the
model can be adjusted accordingly. It is widely understood that cracks increase the transport properties
of concrete, creating perfect pathways for gas and liquid transportation, thus, facilitating the ingress of
deleterious species such as CO2 or chlorides into concrete and accelerating the initiation time for the
corrosion of the steel reinforcement. The estimation of the life span of reinforced concrete structures
having cracks is influenced by characteristics, such as crack width and length, in addition to the
concrete properties and the environmental exposure conditions. The models presented briefly in the
current study to estimate the service life of reinforced concrete structures (as far as chloride ingress
and the action of carbon dioxide from the atmosphere is concerned), take under consideration
parameters influenced by the appearance of cracks on the concrete cover. Research has shown that the
presence of cracks increases the diffusion coefficient of both chloride ions and carbon dioxide. A
comparison of chloride diffusion coefficients for cracked and uncracked concrete showed an increase
in the diffusion coefficient for cracked concrete by one or two orders of magnitude (Raharinaivo et al.
1986, Sahmaran et al. 2007), while a crack width of 0.2 mm was found to increase the carbon dioxide
diffusion coefficient about three orders of magnitude compared to an average quality crack-free
concrete (Alekseev and Rosenthal, 1976). In the model, by adjusting the values of the effective
chloride and/or carbon dioxide diffusion coefficients and by taking under consideration the initial
conditions (Cl- concentration of the surface, environmental exposure, etc.), an initial profile
corresponding to a cracked concrete surface is created, which will be used by the model as a starting
point on the calculation of the service life estimation parameters.
2.4.3 Cost and environmental aspects
Cost and environmental aspects regarding concrete composition are also addressed. As it is the main
aim of the current study to elaborate in detail on these features of the model especially the
environmental aspects, for reasons of completeness a very brief introduction is given herein (please
see more details in Chapter 3).
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J.G. Tapali
In terms of economic cost, the concrete production cost KT (/m3) is calculated (per volume unit of 1
m3 of fresh concrete) by taking into account factors as materials purchasing cost (KP, /m3), mixing
cost for concrete production (KM, /m3), cost of transportation and delivery (KB, /m3), and other
operational costs (KG, /m3), as it shown in the following equation.
KT K p K M K B K G
P (2.7)
CU C SU S FU F AU A WU W DU D PM t M U E K T B U E K G
Q
where, UC,S,F,A,W,D, are the cement, silica fume, fly ash, aggregate, water, admixtures values (/kg),
C, S, F, A, W, D, are the cement, silica fume, fly ash, aggregate, water, admixtures content
(kg/m3 of concrete), PM the mixing power / m3 of concrete (J/s.m3), UE the cost of energy
(/J), tM the mixing time (s), KT the cost of transportation (/m3), PB the pumping power
(W), Q the concrete flow (m3/s).
It should be noted that in the calculation of the concrete mixing cost, the parameters PM and tM depend
on concrete workability and density and, therefore, on concrete composition parameters. The cost of
transportation KT depends on the distance between project location and plant, hence is independent of
concrete compositional parameters. At the project location, the cost is burdened with pumping and
application expenses. Fixed and operational costs include the fixed cost of purchase and establishment
of equipment (depreciation values), labor and administration costs and general operational costs.
In terms of environmental cost (see Chapter 3), the CO2 emissions from concrete production can be
expressed as the summation of the emissions from, the chemical conversion process in clinker
production (during cement manufacturing), from the energy consumption due to fossil fuel
combustion (also during cement manufacturing), from the electrical energy required for the grinding
of any additive materials and from the energy required (in terms of fuel consumption) for the
transportation of the raw materials and of the final product. A more precise estimation of the
environmental footprint of concrete Econc, taking under consideration the environmental factors of each
individual concrete component, based on a large set of concrete production data (from the literature
and from cement production companies) can be expressed as:
Econc = CEc + SES + FEF + AEA + WEW + DED (2.8)
where, C, S, F, A, W, D are the cement, silica fume, fly ash, aggregate, water and admixtures
content (kg of material / m3 of concrete), EC, ES, EF, EA, EW, ED, are the environmental costs
of cement, silica fume, fly ash, aggregates, water and admixtures respectively (kg of CO2 /
kg of material).
70
The above approach introducing the environmental cost indicator is the contribution of the present
Thesis in this prediction tool as well as the overall optimization process (see Chapter 3).
2.4.4 Validation and verification
Having presented the structure and the concept behind the modeling of the physicochemical processes
leading to concrete deterioration, the results of a wide validation study (Papadakis and Demis 2011), in
terms of carbonation exposure, are given in this section. A comparison between experimental
measurements and model predictions of chloride concentration for various concrete specimens has
been presented elsewhere (Papadakis 2000). Currently, an ongoing field study is taking place, for a
thorough validation based on data derived from structures showing signs of chloride induced
corrosion. In the case of carbonation exposure, such a study has been completed and the validation
results are briefly presented bellow.
Carbonation depth results were collected from the recent published literature, under either accelerated
conditioning or natural ageing, for different exposure times. Parameters as cement type, mix design
characteristics, chemical composition of the clinker and pozzolanic materials, levels of relative
humidity and carbon dioxide concentration (where the reinforced concrete element was exposed) were
recorded and inserted into the model. The calculated carbonation depth values were compared with the
corresponding values taken from the literature (see Fig. 2.6). A very good correlation was observed
(an average variation of 7.6 % was calculated).
30
Calculated Carbonation Depth (mm)
Khunthongkeaw et al. 2006

25
Jiang et al. 2000
Atis, 2003
20
Valcuende and Parra, 2010
Balayssac et al. 1995
15
Sisomphon and Franke, 2007
Sanjuan at el. 2003
10
Marques and Costa, 2010
Ann et al. 2010
5
Dinakar et al. 2007
De Ceukelaire and Van Nieuwenburg, 1993
0
0 5 10 15 20 25 30
Experimental Carbonation Depth (mm)
Figure 2.6 Comparison of calculated to experimental carbonation depth values (Papadakis and
Demis 2011).
71
J.G. Tapali
Carbonation Depth (mm)

7
6 w/c 0.55
5
3
w/c 0,45 - Valcuende & Parra 2010
2
w/c 0,45 - Model
w/c 0.45 w/c 0,55 - Valcuende & Parra 2010
1
w/c 0,55 - Model
0
0 10 20 30 40 50
Time of Exposure (months)
Figure 2.7 Calculated and experimental carbonation depth values for different W/C ratios of a CEM
II/B-M type of cement (Papadakis and Demis 2011).
From the characteristic data given in Table 2.2 it can be seen that the model yields very accurate
predictions for a range of both accelerated (up to 1 year) and natural exposure times (up to 18 years,
where considering the experimental value of 11.62 mm with a standard deviation of 2.45, the 8.3 mm
calculated is a very good approximation) and for different cement and concrete compositions. In Fig.
2.7, just as a representative example, an excellent agreement between calculated and experimental
values is observed, for a longer natural exposure time (up to 4.5 years) and for different W/C ratios.
Table 2.2 Characteristic estimated and measured carbonation depth values (Papadakis and Demis
2011).
Reference Cement type RH CO2 Exp. Xc Calc. Xc Exposure

w/c (%) (%) (mm) (mm) Time
Khunthongkeeaw et al. 2006 CEM I 0.67 72.5 0.0625 5.68 5.30 2 year
Sisomphon & Franke 2007 CEM I + fa 0.68 65.0 3 7.50 7.80 4 weeks *
Sisomphon & Franke 2007 CEM I + fa 0.68 65.0 3 11.0 11.7 9 weeks *
Ann et al. 2010 CEM I 0.45 60.0 0.08 11.62 (2.45) 8.30 18 years
Valcuente & Parra, 2010 CEM II/B-M 0.55 60.8 0.035 3.50 3.80 9 months
Valcuente & Parra, 2010 CEM II/B-M 0.55 60.8 0.035 8.40 8.30 42 months
Balayassac et al. 1995 CEM II/B-L 0.48 60.8 0.035 3.00 2.60 6 months
Marques and Costa, 2010 CEM II/A-L 0.60 65.0 5 15.0 15.9 42 days *
Dinakar et al. 2007 CEM II/A-V 0.54 65.0 5.0 5.71 5.6 1 year *
Sisomphon, 2007 CEM III/B 0.60 65.0 3 16.00 15.0 9 weeks *
Marques and Costa, 2010 CEM IV/B 0.55 65.0 5 19.50 18.4 42 days *
*
denotes accelerated exposure
72
In addition, data from a set of characteristic structures showing signs of carbonation-induced

deterioration were derived. Using the simulation tool (EUCON), based on information as, the age they
were erected, their environmental exposure, the type of cement used and the concrete compressive
strength measured, the carbonation depth was estimated and a very good correlation (average variation
of 7.2 %) was observed (Fig. 2.8, Table 2.3).
Table 2.3 Characteristic estimated and measured carbonation depth values from field studies.
Age Carbonation Depth (mm)

Structure
(years) Measured Calculated
1 Industrial facility, Patras, Greece (mortar coating) 70 8 6
Industrial facility, Patras, Greece (no mortar
1 coating) 70 20 19
2 School, Mesologi, Greece 66 45 43
3 Hospital, Lixouri, Greece 51 43 41
4 Town Hall, Voia, Greece 38 35 32
5 Cooling Tower, Megalopolis, Greece (internal) 25 2 2
5 Cooling Tower, Megalopolis, Greece (external) 25 18 16.9
6 School, Nafpaktos, Greece 30 52 50.5
7 Hotel, Galatas, Greece 37 30 32
8 City Hall, Sami, Greece 40 55 50
100
Measured Carbonation Depth (mm)
90
Structure 1
80
Structure 2
70
Structure 3
60
Structure 4
50
Structure 5
40
Structure 6
30
Structure 7
20
Structure 8
10
0
0 20 40 60 80 100
Calculated Carbonation Depth (mm)
Figure 2.8 Comparison of calculated to measured carbonation depth values from field studies (see
Table 2.3).
73
J.G. Tapali
2.5 Life cycle analysis for constructions
Life-cycle analysis (LCA) is a process whereby the material and energy flows of a system are
quantified and evaluated. Environmental life cycle analysis for constructions can actually access the
environmental burden caused by buildings and show measures of reduction as well. Moreover,
numerous environmental assessment tools have been developed to allow scientists analyze the
environmental performance of buildings (see Chapter 1).
LCA focuses to quantify the full range of environmental impacts associated with a product by
considering all inputs of resources and materials and all outputs of wastes and pollution at each stage
of the product's life including acquiring raw materials (e.g., mining), manufacturing and
distributing the product, the consumer's use and maintenance of the product, and its ultimate disposal
(Dimoudi and Tombra 2008).
Fig. 2.9 shows the system boundary in a life cycle analysis which means the inputs and outputs and of
course all the intermediary stages that must be taken into account.
INPUTS Raw materials OUTPUTS

acquisition
Manufacturing, USABLE
processing and PRODUCTS
ENERGY formulation
WATER
Distribution and EFFLUENTS
transportation
WATER
AIRBORNE
Use, reuse and EMISSIONS
maintenance
RAW
SOLID WASTES
MATERIALS
Recycle
OTHER
Waste ENVIRONMENTAL
management RELEASES
SYSTEM BOUNDARY
Figure 2.9 Life Cycle Analysis (LCA) scheme.
74
Life cycle assessment involves three stages:

1. An inventory of materials and energy used and environmental releases from all stages in the
life of a product or process.
2. Impact assessment examining potential and actual environmental and health effects related to
the use of resources (materials and energy) and environmental releases.
3. An improvement assessment, identifying the changes needed to bring about environmental
improvements in the product or process.
TheLifeCycleConcept(forenvironmentalcost)
InitialConstruction
Cost Rehabilitation
Maintenance
Time Salvage
NetPresentValue(forenvironmentalcost)
Thecostofallactivities
arecomputedattime=0
InitialConstruction accountingfordiscountrate
andtime.Thisiscalledthe
NetPresentValue.
Net
Present Rehabilitation
Value
Maintenance
0
Time Salvage
Figure 2.10 The life cycle concept and the calculation of the net present value for environmental
cost.
75
J.G. Tapali
Especially, for a construction or building, the phases of the initial construction, rehabilitation,
maintenance and salvage should be analysed in details, as well as the total service lifetime should be
estimated, see Fig. 2.10. The initial construction includes energy, water and raw materials
consumption as well as the several rehabilitation and maintenance actions during the constructions
service life; whereas during demolition phase some materials could be regained. All these actions can
be characterized by a total cost in terms of CO2 emissions, grey energy consumed, or by economical
terms. The net present value (NPV) of this cost can be calculated by Eq. (2.9) representing the net
fixed environmental cost and having as units CO2 emissions, grey energy consumed, or economical
units.
N
NPV IC RCk / 1 i nk (2.9)
k 1
where, IC the initial cost, RC the recurring costs, N the number of recurring costs, i the discount
rate, nk the number of years when the k recurring cost happens.
In the above fixed environmental cost the operational environmental costs should be added by using
the net present value concept as well. These costs refer to the use of the construction or building, i.e.,
the electricity or other energy sources consumed during operation, heating, ventilation and air
conditioning (HVAC systems), cooking, washing, etc. However, their analysis and estimation are
outside of the scope of the present study.
The total service life time of the construction or building is calculated by the models and the tools
presented in section 2.4, where the concept and the main principles of a software tool (based on
deterministic proven predictive models) for the estimation of concrete service life, are presented. The
tool presented offers a comprehensive approach on concrete service life estimation, in terms of:
Defining the concrete mix design and the main chemical/volumetric characteristics of
concrete.
Estimating the compressive strength class
Accurately predicting the concrete service life, for carbonation and chloride exposure, by
taking under consideration the relative exposure classes and by utilising proven predictive
mathematical models of the physicochemical processes leading to such deterioration.
In the next Chapter (Chapter 3), the environmental cost for concrete production will be analysed,
quantified and optimized by using the above software tools and models.
76
Chapter 3. Environmental cost of concrete production

Estimation & optimization
3.1 Introduction
Today, the cement and concrete industry is still the dominant type of materials industry within the
construction sector. As referred in the Introduction, concrete is recognized to be the most widely used
construction material of nowadays with huge quantities consumed by our society. It has been
estimated that its average consumption is about 1 ton per year per every person on the planet (Flower
and Ganjayan 2007). Despite the economical crisis, previous studies from CEMBUREAU (2011)
showed a 0.7% rise in the EU construction activity in 2011, with the index of cement manufacturing
showing a positive trend. It is predicted that global demand for cement is expected to rise 4.1% yearly,
to 3.5 billion metric tons in 2014.
Such levels of demand however, are associated with significant environmental burden. It is well
known that any type of construction material entails certain aspects of environmental cost (in the form
of carbon dioxide and other gasses emissions and energy consumed) from its manufacturing stage to
its end-use (fixed environmental cost). During concrete production the main emissions to atmosphere
are associated with the cement-making process, where during the stage of clinker formation, CO2 and
other greenhouse gases are emitted to the atmosphere (CEMBUREAU 2009). These types of
emissions are both raw material-related and energy-related. Raw material-related emissions are
produced during limestone decarbonation and account for about 50% - 60% of total CO2 emissions
(Ecosmart Concrete 2008, WBSCD 2005). Energy-related emissions are generated both directly
through fuel combustion and indirectly through the use of electrical power. It is estimated that burning
of 1 ton of clinker releases up to 0.97 tons of CO2 (Habert et al. 2010, IEA 2010). Considering that on
average 900 kg of clinker are used to produce 1 ton of cement, the CO2 emissions per ton of cement
are estimated in the magnitude of 0.87 tons (Ecosmart Concrete 2008, WBSCD 2005). Just to get an
77
J.G. Tapali
indication on the overall magnitude of related emissions, it should be noted that the construction sector
accounts for a considerable share of the total EU final energy consumption (more than 42%) and
produces more than 35% of all the greenhouse emissions (WBSCD 2005, 2009), with cement
manufacturing contributing 5% of the global man made CO2 emissions.
Bearing all of the above in mind, increasing emphasis should be placed on investigating and enforcing
ways and methodologies to make the cement and the construction industry in general a more
environmental friendly sector. On that note, altering the nature of clinker, or reducing the clinker
content of cement with other constituents, should influence directly the levels of the derived CO2
emissions. Several innovative new types of cements with altered clinker properties are being (and have
been) developed, including carbon-negative cement based on magnesium silicates (rather than
limestone as the Ordinary Portland Cement) (Ruffolo et al. 2010), cement produced in a reactor by
rapid calcination of dolomitic rock in superheated steam (Sweeny and Sceats 2009) and cement based
on a mixture of calcium and magnesium carbonates and hydroxides (Bren 2011), with however limited
appeal on the cement manufacturing companies. Reasons for such a withheld acceptance can be found
on the fact that it is estimated that their substantial benefits on the reduction of the associated
emissions will by fully utilized in a time frame of 5-10 years from today (WBSCD 2005, 2009).
Overall, they do not provide a feasible economical and operational solution on tackling the
environmental burden of cement manufacturing, today.
What is actually promising is direct reduction (up to a certain extent) of the clinker content in cement
through utilization of industrial by-products as supplementary cementing materials SCM (fly ash,
silica fume, rice husk ash, ground granulated blast-furnace slag, etc.). It has been estimated that 18%
replacement of Portland cement results in a 17% reduction of the CO2 emissions and that, if just 30%
of cement (Ecosmart Concrete 2008) used globally were replaced with SCMs, the rise in CO2
emissions from cement production could be reversed (see Fig. 3.1).
However, equally important on achieving a green mix design, by utilizing industrial by-products as
cement replacement materials, is to be able to further fine tune this particular mix design in order to
safeguard certain concrete strength and service life requirements. The challenge is to be able to
guarantee not only reduced environmental contribution but also, accepted mechanical properties,
workability, strength development and service life of a structure utilizing an environmentally friendly
cement type.
78
Chapteer 3 - PhD Disssertation
Figure 3.1
3 Effect off SCM utilizaation in CO2 emissions (E
Ecosmart Concrete 2008)).
Previouss research sttudies (Antioohos et al. 2007,

2 Demiss and Papadaakis 2012, P
Papadakis an
nd Demis
2013) haave identifiedd the high addded values of
o SCM inco
orporation in concrete streength and seervice life
under haarsh environm
mental factorrs. Considerable amountt of work on developing analytical models
m for
the evaluuation of SC
CM in concreete using the concept of efficiency
e facctors (or k-values, to com
mpare the
relative performancee of supplem
mentary cem
menting matterials on cooncrete duraability) by Papadakis
P
(1999a, 1999b, Papaadakis et al. 2002) has identified
i th
he high-addedd value of ccertain types of these
materialss (as Type II additives in CEM I typpe of cemen
nt) and their pozzolanic pproperties on
n cement
and morrtar and the effects
e they entail
e on earrly concrete strength
s hos et al.
and volume stabbility (Antioh
2007, Paapadakis andd Tsimas 20022).
What iss needed is to

t be able too achieve an
n optimum, balanced ap
pproach, beetween susta
ainability
and durrability desiggn of reinforrced concrete structurees, an effort put by the p
present Thesis. After
all, the very definittion of sustaainability (C 643 2011) as the abbility of a system
CEN EN 156 s (a
structuree) to be mainntained for the
t present and
a future geenerations incorporates
i to a great ex
xtend the
end resuult of the durability desiggn (maintenannce of a stru
ucture for thee present andd future). It should
s be
noted, thhat the linkagge between durability
d andd sustainabillity is also em
mphasized, oon the newly
y imposed
EN Stanndards on thee sustainable assessment of buildings (CEN EN 15643 2011), where a com
mbination
o environmental and ecoonomic perfo
of the asssessments of ormance taking into accoount the techn
nical and
functionaal requiremeents of a buiilding is appproached, and
d on the nexxt generationn structural codes
c (fib
2010), where
w repair and maintennance of conncrete structu
ures, will bee subjected tto strict requ
uirements
79
J.G. Tapali
both with regard to environmental, economical and service life constraints.
The question that needs to be answered is how their relationship is affected. How a 30% reduction in
clinker content (for example) or a reduction in the overall cement or water content affect the service
life of a structure? Does an accepted sustainable design (from an environmental aspect point of view)
provides automatically a durable design that meets certain target values, or certain modification in the
mix design have to be made (and to what extent)?
The scope of this particular study is to provide answers to the previously mentioned questions, on the
relation between sustainable and durable design of reinforced concrete. To achieve this, a (4-step)
structured methodology is proposed on estimating the reduction of environmental cost (in principle)
and the strength and service life of concrete incorporating cement replacement materials, aiming to
achieve the best possible (optimum) mix design configuration. Although the previously mentioned
methodology is presented in detail in Section 3.3 of this chapter, it can be summarized as follows.
Upon defining a set of design parameters, in terms of concrete compressive strength and service life, a
typical (referenced as control) mix design (no SCM) is selected that produces strength and service life
values higher than the design parameters, but at a high environmental cost. The aim is to reduce
considerable that cost, without compromising on strength or service life. To achieve this, a particular
SCM is utilized at certain incremental percentages and the environmental and service life properties
are calculated. On reaching a rate of pozzolanic reaction bellow 1, further fine-tuning of the concrete
compositional parameters is achieved resulting in reduced environmental cost and at the same time
strength and service life values higher than the predefined ones. As it is also mentioned in Section 3.3,
on every step, the service-life, and compressive strength, evaluation was made using a software tool
(EUCON), based on proven predictive models (according to performance-related methods for
assessing durability) developed and validated elsewhere (Papadakis and Efstathiou 2005, Demis and
Papadakis 2012, Papadakis et al 1991, 2007, Papadakis and Demis 2013) well published and awarded
by the ACI, for the estimation of concrete service life when designing for durability under harsh
environments.
On this note, fly ash and silica fume were evaluated as Type II additives on a common CEM I type of
cement. The first step however is the estimation of the environmental output of concrete incorporating
these types of materials, as it illustrated in the following section.
3.2 Estimation of environmental cost of concrete
It was previously mentioned that during the concrete production the main emissions to air are
80
associated with the cement manufacturing process. However, other concrete constituents also
contribute in that sense. In general, it can be said that the CO2 emissions from concrete production are
the summation of the emissions from, the chemical conversion process in clinker production (during
cement manufacturing), from the energy consumption due to fossil fuel combustion (also during
cement manufacturing), from the electrical energy required for the grinding of any additive materials
and from the energy required (in terms of fuel consumption) for the transportation of the raw materials
and of the final product. Overall, the initial environmental cost of concrete EI,conc (expressed in kg CO2
/ m3 of concrete) taking under consideration every environmentally contributing parameter from the
materials supply to concrete production, delivery and casting can be expressed as:
EI,conc = EM + EP + ET + EG (3.1)
where EM is the environmental cost of materials, EP the environmental cost for concrete production, ET
the environmental cost for concrete transportation and delivery, and EG the cost for concrete casting,
placing and finishing (all expressed in kg CO2 / m3 of concrete).
A more precise estimation of the environmental footprint (environmental factors) of each individual
concrete component, based on the literature and on data derived from a Greek cement manufacturing
company, is presented in this section. The total fixed environmental footprint of concrete materials (EM,
kg CO2 / m3 of concrete) can be calculated as:
EM = CEc + (SCMESCM) + AEA + WEW + DED (3.2)
where C, SCM, A, W, and D: are the contents (in kg / m3 of concrete) of cement, supplementary
cementing materials, aggregate, water and admixtures, respectively, in the concrete volume, and EC,
ESCM, EA, EW, and ED: their corresponding environmental costs (in kg of CO2 / kg of material).
By taking under consideration the chemical equation of complete combustion of coal (Eq. 3.3), where
94 kcal/mol of energy is produced (Q), since it is an exothermic reaction, the amount of CO2 produced
from energy consumption of 1kWh is calculated as 0.404 kg (1 cal is equal to 1.162 10-6 kWh, hence
94 kcal equal to 0.109 kWh producing 44 g of CO2).
C + O2 CO2 + Q (3.3)
The related to cement production CO2 emissions vary from 0.65-0.92 tons per ton of cement produced
based on a cement plant with a modern technology and equipment, according to the literature (Flower
and Ganjayan 2007, Hoenig et al. 2007), or from 0.61 0.80 according to data from cement
81
J.G. Tapali
manufacturing companies (ACC 2010, CRH 2011, Heidelberg Cement 2009, Holcim 2011,
Italcementi Group 2011, Lafarge 2011) (see Table 1). It should be noted that the levels of CO2
emissions derived from cement manufacturing companies (Table 3.1) represent the average levels of
emissions produced of the total range of different cement types produced annually by each company.
Hence, they do not reflect on the actual levels of emissions of a CEM I type of cement.
Table 3.1 Cement production data and CO2 emissions from the industry (ACC 2010, CRH 2011,
Heidelberg Cement 2009, Holcim 2011, Italcementi Group 2011, Lafarge 2011).
Cement Electrical Energy CO2 Emissions

Reference Produced Consumed (t/year) (t/t cement)
(million t/year) (kWh/t cement)
CRH 2011 15.6 180 10.3 * 106 0.735
6
Heidelberg 2009 3.90 131 3.70 * 10 0.739
6
Holcim 2011 144.3 100 102. * 10 0.608
Italcementi 2011 71.8 122 34.4 * 106 0.708
Lafarge 2011 145 - 98.0 * 106 0.611
6
ACC 2010 - 118 43.1 * 10 0.798
For the purposes of this study, based on operational and production data from the Greek cement-
manufacturing company, the level of CO2 emissions from cement manufacturing was accurately
estimated. By taking into account data as, the amount of cement produced (1,700,000 t/year), the
electrical energy required (500,000 kWh/day) the level of CO2 emissions measured (3,801,000 kg/day)
and the total days of operation per year (335), the total CO2 emissions were calculated to be in the
range of 1,341,005 t/year. Hence in order to produce 1 t of cement 0.79 t of CO2 are emitted into the
atmosphere. In addition to the later, the derived CO2 emissions from transportation should be added.
Considering that on average 2.74 kg of CO2 is emitted per litre of fuel, using vehicle transport, and
that fuel consumption is estimated to be 1 lt / 3 km for 5 t of raw materials, the overall emissions arise
from transportation are estimated to be 0.183 kg / km / t of raw material (GHG Protocol 2001).
According to data from a cement manufacturer (ItalCementi 2011), in order to extract, process and
grind aggregates the overall CO2 emissions are estimated to be 5.96 kg / t of aggregates (considering
that 2.53 kWh are required for the production of 1 ton of aggregates and that 9 lt of fuel are required
for the transportation of a 5 tons shipment, resulting in 4.94 kg of CO2 / t of aggregates).
82
When fly ash is used as an SCM, since it is a by-product of coal burning in electrical power stations,
the emissions associated with power generation are not considered of being part of the environmental
burden of fly ash. A small amount of energy required for the grinding of the raw material into very fine
powder and for its transportation are the only sources of greenhouse gasses. According to the literature
(IPPC 2010, US Environmental Protection Agency 2008) the previously mentioned energy
requirement is estimated to be in the order of 20 kWh per ton of fly ash produced, hence 8.06 kg of
CO2 per ton of fly ash (emissions from transportation, similar to cement transportation, should also be
added). In the case of silica fume, since it is available from limited regions on European level, the
related emissions arise from its transportation. For reasons of simplicity, since the aim of the current
study is to produce an estimation of the environment impact of concrete the previously mentioned
source of emissions are assumed to be twice of those of fly ash transportation.
As far as water is concerned, the only source of emissions arises from the electrical energy required to
pump the water, which in this study is considered to be negligible. Since no admixtures were used on
the mix design of the different concrete configurations used in this study, the environmental impact of
admixtures is ignored.
In this way, based on the proportions of the concrete constituent materials used and on the
environmental factors, as derived above, the overall environmental cost of concrete was calculated.
These calculations were incorporated on every step of the structured methodology presented in the
following section.
3.3 Structured methodology for concrete mix design optimization
A schematic illustration of the (4-step) methodology proposed in this study, for the evaluation of the
effectiveness of industrial by-products as cement replacement materials in achieving a robust mix
design (in terms of concrete properties and service life) with minimum environmental cost is presented
in Fig. 3.2.
The concept can be briefly described as follows:
For given design parameters, as concrete compressive strength and service life (e.g. 40 MPa and 50
years), an initial set of concrete compositional parameters (CCP; cement, water, aggregate) is
selected (achieving the target values) but with an initial high environmental cost (Step 1). This
particular mix design is referenced as the control mix (with 95% clinker, no SCM) and its
corresponding properties as the control values (strength, service life, environmental cost).
83
J.G. Tapali
A particular SCM is utilized as cement replacement material (Step 3) at a certain percentage (e.g.
10%, 20%, 30% for fly ash and 5%, 10%, 15% for silica fume, since it is a more intense pozzolanic
material than fly ash). The environmental cost and the corresponding concrete properties are
calculated, per incremental step of SCM addition. In order to provide a level of comparison in
terms of concrete properties of the utilization of SCM (with the control mix, from step 1), these
materials are also inserted in the mix as aggregate replacement materials (Step 2). Eventhough they
do not replace cement, hence we do not achieve a reduction in environmental cost, at the same time
we do not particularly increase it, since the aggregate associated levels of CO2 emissions are very
small (5.96 kg / t of aggregates).
Based on the best performed mix design configuration from Step 3 (in terms of environmental cost
and target values) further reduction in the CCP properties is achieved (Step 4), through incremental
reductions of cement (10 kg per step) and water (10 kg per step, for each decrease in cement
content). In essence we are altering the water-to-cement (w/c) ratio of the best performed mix at
Step 3, keeping at the same time the percentage of SCM constant.
In terms of service life as indicators of performance, the critical time for initiation of corrosion due to
the action of carbon dioxide from the atmosphere (and the corresponding depth of carbonation), as
well as the critical time for initiation of chloride induced corrosion (and the adequate concrete cover
needed in order to sustain a chloride free concrete cover for a period of 50 years), were selected.
On every step, the service-life, and compressive strength, evaluation was made using a software tool
(EUCON), based on proven predictive models (according to performance-related methods for
assessing durability) developed and validated elsewhere (Papadakis and Efstathiou 2005, Demis and
Papadakis 2012, Papadakis et al 1991, 2007, Papadakis and Demis 2013) well published and awarded
by the ACI, for the estimation of concrete service life when designing for durability under harsh
environments. Concrete service life is reliably predicted using fundamental mathematical models that
simulate the basic deterioration mechanisms of reinforced concrete (carbonation, chloride penetration).
Principles of chemical and material engineering have been applied to model the physicochemical
processes leading to concrete carbonation, as well as the processes of chloride diffusion in the aqueous
phase of pores, their absorption and binding in the solid phase of concrete and their desorption.
84
Figure 3.2 Logical diagram of structured methodology for obtaining CCP values for minimum
environmental cost (EC) with optimum strength and durability properties (C, P, W: cement,
SCM and water contents, in kg/m3; Zcarb, ZCl-: service life in carbonation and chloride
exposure, in years)
3.4 Utilization of structured methodology for concrete mix design optimization
3.4.1 Step 1: Selection of initial CCP values
A compressive strength of 40 MPa and a service life of 50 years were selected as the defined target
values. A typical CEM I mix (w/c: 0.5, cement content: 300 kg/m3, crushed aggregates of 31.5 mm
maximum size, no additives, no admixtures), water cured for 28 days, was selected as the control mix.
Its overall environmental contribution was calculated to be 311.47 (kg CO2/m3 of concrete). The
control mix produced a concrete compressive strength of 44.6 MPa and gave a service life of 119.9
years under carbonation exposure (for a concrete cover: 30 mm) and 53.1 years under chloride
85
J.G. Tapali
exposure (for a concrete cover: 30 mm). These values (environmental cost, strength and service life)
are regarded as the reference (control) values on every mix design optimisation procedure followed in
the current study.
3.4.2 Steps 2 and 3: Replacing aggregates or cement by SCM
On every mix design a constant volume unit (1 m3) of concrete was chosen as a common basis. When
an SCM was added to this unit, then an equal volume of another component, either cement (Step 3) or
aggregate (Step 2), was removed in order to keep the same total volume and the common comparison
basis. Several mix design configurations were considered (see Table 3.2), where each time addition of
a Type II additive took place, at certain proportions, as cement and as aggregate replacement.
Table 3.2 Mix design, service life indicators and environmental cost (Steps 1-3).
SCM SCM C W A P fc Zcarb ZCl- EC EC

w/c kg CO2
type % kg/m 3
kg/m 3
kg/m 3
kg/m 3
MPa years years
/m3 con.
%
Control 0 300 150 0.5 1925 - 44.6 119.9 53.1 311.47 -
SFA Replacing aggregates
s-fa 1a 10 300 150 0.50 1890 30 47.4 175 187.5 311.52 0.02
s-fa 2a 20 300 150 0.50 1856 60 50.3 >200 >200 311.58 0.03
s-fa 3a 30 300 150 0.50 1821 90 50.4 >200 >200 311.63 0.05
Replacing cement
s-fa 1c -10 270 150 0.56 1915 30 41.8 98.4 81.3 281.67 -9.57
s-fa 2c -20 240 150 0.63 1905 60 38.0 74.3 106.3 251.87 -19.14
s-fa 3c -30 210 150 0.71 1895 90 31.7 47.6 45.8 222.07 -28.70
CFA Replacing aggregates
c-fa 1a 10 300 150 0.50 1896 30 51.4 180.2 118.8 311.56 0.03
c-fa 2a 20 300 150 0.50 1866 60 58.0 > 200 >200 311.64 0.05
c-fa 3a 30 300 150 0.50 1837 90 64.4 > 200 >200 311.72 0.08
Replacing cement
c-fa 1c -10 270 150 0.56 1920 30 45.8 102.3 70.8 281.70 -9.56
c-fa 2c -20 240 150 0.63 1916 60 46.9 86.2 93.8 251.94 -19.11
c-fa 3c -30 210 150 0.71 1911 90 48.0 72.2 187.5 222.16 -28.67
SF Replacing aggregates
sf 1a 5 300 150 0.50 1908 15 50.8 135.3 137.5 311.39 -0.03
sf 2a 10 300 150 0.50 1890 30 56.9 146.5 >200 311.30 -0.06
sf 3a 15 300 150 0.50 1873 45 62.0 164.8 >200 311.21 -0.08
Replacing cement
sf 1c -5 285 150 0.53 1920 15 48.0 102.9 81.3 296.46 -4.82
sf 2c -10 270 150 0.56 1915 30 51.4 85.2 143.8 281.45 -9.64
sf 3c -15 255 150 0.59 1910 45 51.2 70.9 156.3 266.43 -14.46
SCM: Replacement level (%) with supplementary cementing material
C: cement content (kg/m3) W: Water content (kg/m3)
A: aggregate content (kg/m ) 3
w/c: Water/cement ratio
SCM content (kg/m3) of fly ash FA (siliceous SFA or calcareous CFA) and of silica
P:
fume SF
fc: Concrete compressive strength (MPa)
Zcarb, ZCl- Service life for carbonation and chloride exposure, respectively (years)
EC, EC: Environmental cost (kg CO2 / m3 of concrete) and change (%) compared to control
86
In the case of fly ash, 10, 20 and 30 % replacement levels of the control cement mass were chosen,
while in the case of silica fume, since it is a more intense pozzolanic material than fly ash (hence the
degree of pozzolanic reactions drops bellow one for lesser quantities than fly ash) 5, 10 and 15%
replacement levels were used. The water content (kg/m3) was kept constant for all specimens.
Overall, in terms of concrete and durability properties, it was seen (Tables 3.2 and 3.3) that when
SCM was used for cement or aggregate replacement, the derived strength and service life values were
higher than the target values initially set (40 MPa and 50 years). When SCM was used as aggregate
replacement, incorporation of calcareous fly ash (CFA) in CEM I type of cement produced a better
performance than siliceous fly ash (SFA) (Fig. 3.3). Addition of 30% of CFA produced similar service
life (more than 200 years for carbonation exposure) values to SFA but increased the compressive
strength considerably higher (Table 3.3) than SFA, compared to control (44.4% strength increase for
CFA, compared to 13% increase for SFA).
Additionally and more important the derived strength values were 61% and 26% higher than the target
strength value initially set (40 MPa) in the case of CFA and SFA correspondingly. Silica fume (SF)
although it produced concrete and durability values higher than the target set values, compared to FA
it did not proved to be as effective in inhibiting carbonation exposure. The service life was increased,
but to a lesser extent. To draw a level of comparison between performances, 10 % addition of SF
increased the service life for carbonation by 22.2% (compared to the control value of 119.9 years of
the control mix), compared to the 46% and 50.3% increase observed when 10% of siliceous and
calcareous fly ash was added.
Service Life for Chloride Exposue (years)
Concrete Compressive Strength (MPa)
70 250
SFA
60
CFA 200
SF
50
150
40
Target Value of 40 MPa
30 100
20 Target Value
of 50 years
50
10
Replacing Cement Replacing Aggregates Replacing Cement Replacing Aggregates
0 0
-40 -30 -20 -10 0 10 20 30 40 -40 -30 -20 -10 0 10 20 30 40
SCM (%) SCM (%)
Figure 3.3 Comparison of SF and FA performance in terms of target values for strength (left) and
service life for chloride exposure (right).
87
J.G. Tapali
Table 3.3 Comparison of strength and servie life values to initial set target values (Steps 1-3).
Zcarb ZCl-
SCM fc > > set > set
type SCM fc fc set value Zcarb Zcarb value ZCl- ZCl- value
% MPa % % years % % years % %
Control 0 44.6 - - 119.9 - - 53.1 - -
SFA Replacing aggregates
s-fa 1a 10 47.4 6.3 18.5 175 46.0 >150 187.5 252.9 >150
s-fa 2a 20 50.3 12.8 25.8 >200 66.8 >150 >200 276.5 >150
s-fa 3a 30 50.4 13.0 26.0 >200 66.8 >150 >200 276.5 >150
Replacing cement
s-fa 1c -10 41.8 -6.3 4.5 98.4 -17.9 96.8 81.3 52.9 62.5
s-fa 2c -20 38.0 -14.8 -5.0 74.3 -38.0 48.6 106.3 100.0 112.5
s-fa 3c -30 31.7 -28.9 -20.8 47.6 -60.3 -4.8 45.8 -13.7 -8.3
CFA Replacing aggregates
c-fa 1a 10 51.4 15.2 28.5 180.2 50.3 >150 118.8 123.5 137.5
c-fa 2a 20 58.0 30.0 45.0 >200 66.8 >150 >200 276.5 >150
c-fa 3a 30 64.4 44.4 61.0 >200 66.8 >150 >200 276.5 >150
Replacing cement
c-fa 1c -10 45.8 2.7 14.5 102.3 -14.7 104.6 70.8 33.3 41.7
c-fa 2c -20 46.9 5.2 17.3 86.2 -28.1 72.4 93.8 76.5 87.5
c-fa 3c -30 48 7.6 20.0 72.2 -39.8 44.4 187.5 252.9 275.0
SF Replacing aggregates
sf 1a 5 50.8 13.9 27.0 135.3 12.8 >150 137.5 158.8 >150
sf 2a 10 56.9 27.6 42.3 146.5 22.2 >150 >200 276.5 >150
sf 3a 15 62 39.0 55.0 164.8 37.4 >150 >200 276.5 >150
Replacing cement
sf 1c -5 48 7.6 20.0 102.9 -14.2 105.8 81.3 52.9 62.5
sf 2c -10 51.4 15.2 28.5 85.2 -28.9 70.4 143.8 170.6 >150
sf 3c -15 51.2 30.0 28.0 70.9 -40.9 41.8 156.3 194.1 >150
fc: Zcarb ZCl-: Change in concrete compressive strength and service life values compared to control (%)
Percentage of concrete compressive strength and service life above target values set (40
> set value
MPa, 50 years)
In the case where SCM were used as cement replacement materials, the service life to carbonation
exposure was decreased for every type of SCM used. In other words, the corresponding carbonation
depth values calculated by the models utilised in this study were increased, with increasing content of
SCM. As far as chloride exposure is concerned (Fig. 3.3b), specimens incorporating SCM whether
aggregate or cement was substituted, produced increased service life values compared to control.
Silica fume proved to inhibit chloride diffusion more efficiently than FA. A staggering 170% increase
on the service life (compared to control) was noticed for 10% SF utilization, in contrast to 33.3% and
52.9% increases in the cases of CFA and SFA (correspondingly). Is should also be noted, that at
higher levels of SFA (30%) the service life values to both carbonation and chloride exposure dropped
below the target service life value initially set (of 50 years). The reasons for such a performance are
explained in the following section.
88
In terms of environmental performance, utilization of 30% FA, as cement replacement material,

reduced the concrete environmental footprint by 28.7% (to 222.07 kg CO2 / m3 of concrete), compared
to a 14.5% reduction achieved when 15% of SF was utilized. Of course, when SCM were used as
aggregate replacements the environmental output of concrete did not change. A comparative
assessment of every strength, durability and environmental cost indicator, calculated in this study, for
CFA and SF is given in Fig. 3.4. In this way, the reduction of environmental cost observed can be
weighed against the strength and service life values.
Compressive Strength
Service Life for Carbonation
Service Life for Chloride Exposure
Environmental Cost
Service Life for Chloride Exposure (years)

350 70 250 250
Service Life for Carbonation (years)

CFA
Compressive Strength (MPa)
300 60
200 200
(kg CO2 / m3 of concrete)
Environmental Cost
250 50
150 150
200 40
150 30
100 100
100 20
50 50
50 10
Replace Cement Replace Aggregates

0 0 0 0
-40 -30 -20 -10 0 10 20 30 40
Service Life for Chloride Exposure (years)

350 70 250 250
Service Life for Carbonation (years)
SF
300 60
200 200
(kg CO2 / m3 of concrete)
Environmental Cost
250 50
150 150
200 40
150 30
100 100
100 20
50 50
50 10
Replace Cement Replace Aggregates
0 0 0 0
-20 -15 -10 -5 0 5 10 15 20
Figure 3.4 Overall performance of CFA and SF mixes in terms of environmental cost, concrete
strength and service life properties.
It can be seen that even though in terms of environmental cost CFA outperformed SF (28.7% reduction
compared to a 14.5% reduction for SF), in terms of concrete properties SF performed better than FA in
general. A 10% utilization of SF increased the concrete compressive strength by 15.2% (compared to
89
J.G. Tapali
the control value of 44.6 MPa), in contrast to a mere 2.7% increase achieved when CFA was used. In
terms of service life, for chloride exposure each SCM gave comparable significant increases to control.
For carbonation exposure however, the service life was reduced compared to the control value (119.9
years) but remained higher than the target set value (of 50 years) by 41.8% and 44.4% when SF and
CFA were used respectively.
Such a behavior, in terms of reduction in environmental cost and trends in service life and strength was
also noticed for
different w/c ratios (Fig. 3.5a), other than the control value of 0.5, but for the same initial
cement content (300 kg/m3 concrete, as in the control mix),
different initial cement content from (300 up to 400 kg/m3) for w/c ratio of 0.5 (Fig. 3.5b).
100
(MPa)
320
80 (a)
(b)
3 concrete)
rength
300
Cost
60
280
Environmental
Compressive St
40 260
(kg CO 2 / m
20 240
220
0
0,40 200
0,45 0.40 0,40
0,45
w /c
0,50 0.45
0,50
w
0,55 0.50 30 40
/c
0,55
0,60 20 30 40 0.55 10 20
0 10 0,60 0
-10
0,65 -20 -10 0.60
0,65 -20
-40 -30 ) control -40
-30 (%)
SCM (% SCM
250
/m concrete)
ars)
(c)
200 420
re (ye
(d)
3
400 300
150
Chloride Exposu
l Cost (kg CO2
380 320
340
100 360 360
Serv
340 380
50
400
320
control
0
Environmenta
300
0,40
0,45 280
20
0,50 260 15
w
40 10
/c
0,55 20 30 380
360
5)
0,60 0 10 0 (%
-10 340 -5 CM
-20 320 -10 S
0,65 -30 C ( 300
-40 ( %) 280 -15
SCM Kg
/m3 260 -20
)
Figure 3.5 Overall performance of SCM in terms of environmental cost (b), concrete strength (a) and
service life properties (c) for a range of w/c ratios and for different cement content (d).
90
The rate and the overall reduction in environmental cost was very similar on every different mix
design with either different w/c ratio (but for the same cement content) or with different initial cement
content (but for the same w/c ratio), since the cement replacement level follows the same incremental
increase. Overall the 28.7% reduction in environmental cost (in the case of FA) is achievable with a 30%
utilization of SCM as Type II additive (with accepted strength and service life properties).
Considering the fact that at higher SCM replacement levels, the degree of the pozzolanic reaction
drops quickly below one, the question is, how can we further reduce the environmental cost without
compromises on strength and durability properties? Such a solution is attempted on Step 4 of the
methodology previously described (Fig. 3.2) and utilized in this study, for the optimum mix design
configuration in terms of environmental cost at one end and concrete and durability properties at the
other.
3.4.3 Step 4: Further reduction of W and/or C contents
As previously described, on the best performed mix design configuration from Step 3 further reduction
in the CCP properties can be achieved, through incremental reductions of cement (by 10 kg/m3) and
water (per 10 kg/m3), for each decrease in cement content. Overall, we are altering the w/c ratio of the
best performed mix at Step 3, keeping at the same time the percentage of SCM constant.
Such a mix design configuration, in the case of FA utilization, is given in Tables 3.4 and 3.5.
Compared to the initial control mix (0.5 w/c ratio, 300 kg/m3 cement content, no SCM), two CFA mix
designs were further investigated (with 20 % cement replacement by CFA and with 30%, illustrated in
Tables 3.4 and 3.5 respectively). On each SCM mix initially the cement content was reduced by 10
kg/m3, followed by a step by step decrease of the water content by 10 kg/m3. These reductions, were
stopped when either strength or service life values dropped below the target values initially set (40
MPa and 50 years).
It should be noted that such reductions in cement and water content (although have been approached in
the literature, Newlands et al. 2012), might fail to meet certain minimum composition criteria
(minimum cement content, maximum w/c ratio) for certain exposure classes, as defined in the relevant
standard. However, better and more realistic reductions can be achieved if a mix design other than the
control is selected as the base line of comparisons (e.g. with more increased cement content). After all,
the main aim of this study is to demonstrate the effectiveness of altering the concrete compositional
parameters (cement, water, SCM, etc.) in principle, in achieving a reduced environmental cost with
accepted at the same time concrete and service life properties.
91
J.G. Tapali
Table 3.4 Strength and durability indicators compared to initially set target values for strength and
service life, of a 20% CFA mix (Step 4).
fc Zcarb Zcl-
fc Ec
C W A > set Zcarb > set Zcl- > set Ec
3 3 3 kg CO2
kg/m kg/m kg/m MPa value years value years value / m3con
%
% % %
Control mix 300 150 1925 44.6 - 119.9 - 53.1 - 311.47 -
20% 240 150 1916 46.9 17.3 86.2 72.4 93.8 87.5 251.94 19.11
SCM mix
240 140 1942 50.6 26.5 118.1 136.2 187.5 > 150 252.09 19.06
240 130 1967 54.8 37.0 175.4 > 150 262.5 > 150 252.24 19.02
C stable
W-10-40 kg/m3 240 120 1994 59.7 49.5 203 > 150 200 > 150 252.40 18.97
240 110 2020 65.1 62.8 203 > 150 200 > 150 252.56 18.92
230 140 1949 48.6 21.5 95.6 91.2 118.8 137.5 242.13 22.26
230 130 1976 52.8 32.0 136.5 > 150 237.5 > 150 242.29 22.21
C- 10 kg/m3
W-10-40 kg/m3 230 120 2001 57.4 43.5 203 > 150 200 > 150 242.44 22.16
230 110 2028 62.8 57.0 203 > 150 200 > 150 242.60 22.11
200 140 1974 42.7 6.75 53.3 6.6 70.8 41.7 212.28 31.85
200 130 2000 46.4 16.0 71.3 42.6 118.8 137.5 212.44 31.80
C 40 kg/m3
W-10-40 kg/m3 200 120 2026 50.7 26.8 102.4 104.8 200 > 150 212.59 31.75
200 110 2052 55.6 39.0 163.3 > 150 200 > 150 212.75 31.70
170 120 2051 43.8 9.50 51.1 2.2 106.3 112.5 182.74 41.33
C 70 kg/m3
W-10-40 kg/m3 170 110 2077 48.3 20.8 73.3 46.6 200 > 150 182.90 41.28
Table 3.5 Strength and durability indicators compared to initially set target values for strength and
service life, of a 30% CFA mix (Step 4).
fc Zcarb Zcl-
fc Ec
C W A > set Zcarb > set Zcl- > set Ec
3 3 3 kg CO2
kg/m kg/m kg/m MPa value years value years value / m3con
%
% % %
Control mix 300 150 1925 44.6 - 119.9 - 53.1 - 311.47 -
30% 210 150 1911 48 20 72.2 44.4 187,5 > 150 222.16 28.67
SCM mix
210 140 1937 51.8 29.5 97.6 95.2 200 > 150 222.32 28.62
210 130 1963 56.1 40.25 141.7 > 150 200 > 150 222.47 28.57
C stable
W-10-40 kg/m3 210 120 1989 61 52.5 200 > 150 200 > 150 222.63 28.52
210 110 2015 66.5 66.25 200 > 150 200 > 150 222.78 28.47
200 140 1945 49.9 24.75 78.6 57.2 200 > 150 212.37 31.82
200 130 1971 54 35 110.9 121.8 200 > 150 212.52 31.77
C stable
W-10-40 kg/m3 200 120 1997 58.8 47 171.1 > 150 200 > 150 212.68 31.72
200 110 2023 64.2 60.5 200 > 150 200 > 150 212.83 31.70
160 120 2030 46.1 15.25 57 14 200 > 150 172.87 44.50
C stable
W-10-40 kg/m3 160 110 2056 50.6 26.5 78.6 57.2 200 > 150 173.03 44.45
92
A first overall observation is that the environmental cost can be further reduced (up to 44.5%) in
providing a mix design with guaranteed concrete compressive strength above 40 MPa and a service
life of more than 50 years.
A closer look of the environmental and concrete strength and service life values achieved (Table 3.4),
per step by step reductions of cement and water contents, reveals that the further reduction in cement
content is associated with the desirable decrease of the environmental cost of concrete. The associated
water reductions (from 10 to 40 kg/m3) for each step by step reduction in cement content are
associated with the further enhancement of strength and service life properties. Just to emphasize the
validity of this particular point (illustrated in Fig. 3.6) it should be noted that for a 10 kg/m3 reduction
in cement content of the 30% CFA mix (from 210 kg/m3 to 200 kg/m3), the corresponding water
content was reduced from 10 40 kg/m3. Overall, for such a further cement reduction, a 31.7%
decrease (on average) in environmental cost was noted (31.82% and 31.7% for 10 kg/3 and 40 kg/m3
reductions in water content, correspondingly). However, in terms of water content reduction, the mix
design with its water content reduced by 40 kg/m3 provided higher compressive strength and service
life values (especially for carbonation exposure) than any other smaller reduction in water (10 30
kg/m3).
320 Env. cost of control mix (No SCM, C: 300
300
Environmental Cost (kg CO2/m concrete)
280
64.2 MPa 49.9 MPa
>200 75.6 years Env. cost of 20% CFA mix
3
260
(C: 240 kg/m3, CFA: 60
-10 kg/m3)
240
-20
-30
-40
220
-50
-60
200
-70
-80
180
Cement reduction (kg/m3)
160
100 110 120 130 140 150 160
Water Content (kg/m3)
Figure 3.6 Effect of step/step reduction of cement and water contents on the environmental cost of a
20% CFA mix.
93
J.G. Tapali
The best behavior in terms of environmental cost and concrete/service life properties of the further
reduction in cement and water content of a 30% CFA mix is illustrated in Fig. 3.7.
200
Strength andServiceLife
(%)>InitiallySetValues
morethan150%
150
100
60.5 54.5% 68%
57.2%
45.8%
50
26.5%
0
EnvironmentalCost
Reductionin
50
0 10 20 30 40 50 60
(%)
10kg/m3 stepbystepdecreaseofinitialCementContent(kg/m3)
fc(%)>setvalue Zcarb(%)>setvalue
Zcl(%)>setvalue Ecreduction(%)
Figure 3.7 Effect of step by step reduction of cement and water contents on the environmental cost
and strength and service life values of a 30% CFA mix.
It can be seen, how a further (to a 30% replacement by CFA) reduction in cement content alters the
environmental cost of concrete. Furthermore, Fig. 3.7, shows how such a reduction affects strength
and service life compared to the initially set target values (of 40 MPa and 50 years). For example, a
further cement content reduction by 30 kg/m3, on a 30% CFA mix, reduces the environmental cost of
concrete by 38 %. More important is the fact that it provides a concrete compressive strength of 58.3
MPa and a service life in carbonation and chloride exposure of more than 200 years, values higher
than 45.8% and more than 150% compared to the target 40 MPa strength and 50 years service life.
Hence, considerable reductions in environmental cost of concrete can be achieved, without
compromising on strength and service life (in essence on structural safety).
3.5 Discussion
The aim of this study was to investigate the relationship of sustainable and durable design, in terms of
concrete mix proportioning, in providing a valid mix design with accepted strength and service life
properties, but with the minimum environmental cost. To achieve this, a (4-step) structured
94
methodology (Fig. 3.2) was developed. Upon defining a set of target strength and service life values,
an initial mix design is selected with 95% clinker (Step 1). Its strength and service life (in terms of
carbonation and chloride exposure) values are estimated, using proven predictive models developed
and validated by some of the authors of this study. In addition, its environmental output (in terms of kg
CO2/m3 of concrete) is calculated, according to the concept described in section 2 of this study, using
data from the literature and from cement production companies. At the next step, the effectiveness of
SCMs (fly ash and silica fume) as cement (clinker) and aggregate replacement materials (Steps 2 and 3)
is investigated, in reducing the environmental cost and in providing accepted strength and service life
properties. The best performed mix design with a certain percentage of SCM is further optimized (Step
4) in reducing further its environmental output.
When SCM were utilized as aggregate replacement materials (Step 2) their environmental output was
not improved (which is expected since they do not replace clinker). However, the strength and service
life in carbonation exposure were considerably increased, compared to control. When SCM replaced
cement (Step 3), smaller service life and strength values to control (hence larger carbonation depths),
were produced, still higher than the target values set (50 years and 40 MPa) and their environmental
output was considerably reduced (Table 3.2).
Although it has been noted (Atis, 2003) that there is no general agreement as to whether fly ash
utilization tends to lessen the rate of carbonation, similar behavior (in terms of service life values for
cement replacement) as the one observed in this study, has been observed also by other researchers.
Khunthongkeaw (et al. 2006) stated that the carbonation depth increased along with the increase in the
fly ash content (became critical for 30% fly ash). On a similar note, Lo (et al. 2010) observed that at
high PFA replacement levels (more than 40%) carbonation depth was considerably increased. The
explanation for such a behavior, lays in the way these materials were incorporated into the mix. In the
first case (SCM replacing aggregates), the total amount of carbonatable constituents remains almost
the same, resulting in decreased porosity and lower carbonation rates (Papadakis 2000). While in the
second case (SCM replacing cement), by reducing the cement and clinker content, the amount of
carbonatable materials is also reduced (due to the decrease in total CaO), resulting in higher
carbonation rates (Khunthingkeaw et al. 2006; Lo et al. 2009). In general SCM materials (as cement
replacements) proved to be less resistant to carbonation, mainly due to their low binding capacity of
CO2, caused by their smaller concentrations of Ca(OH)2, compared to control (due to the consumption
by pozzolanic reaction, and lower cement content).
Under chloride exposure they all behaved much better than control. It has been noticed that specimens
incorporating an SCM, whether it substitutes aggregate or cement, exhibit significantly lower total
chloride content for all depths from the surface (Chalee. et al 2010, Hosam et al. 2010).
95
J.G. Tapali
Silica fume proved to be most efficient in inhibiting chloride ingress, than fly ash (since a 10%
replacement by SF resulted in a 170% increase of service life compared to control, than the 33.3% and
52.9% for SFA). Silica fume, composed by very small spherical particles, due to its ultra fineness and
activity led to the formation of intense pozzolanic reaction products (with increased chloride ion
binding capacity than fly ash) within the capillary pore spaces and as a consequence, a finer and more
segmented pore system is produced (Hosam et al. 2010; Nochaiya et al. 2010).
When fly ash was used, a study pozzolanic reaction level was observed for calcareous fly ash (rate of
pozzolanic reaction equal to 1) resulting in higher service life to chloride exposure (at high, 30%
concentration level). CFA due to its high calcium oxide content, apart of being pozzolonic active,
reacts faster than siliceous reach cement replacement materials, since it contains higher amounts of
aluminate-cementing compounds (C3A, C4AF), leading to a more increased chloride ion binding
capacity. On the contrary, when siliceous fly ash was used smaller than the control values (in both
strength and service life) were obtained. Such a behaviour, can be explained by the very nature of a
rich in silica material. In general, when pozzolanic materials with high active silica content are added
to cement, the silica (SiO2) present in these materials reacts with free lime released during the
hydration of cement and forms additional calcium silicate hydrate (CSH) as new hydration products
which improve the mechanical properties of concrete formulation (Ganesan and Thangavel 2007).
However when all the available free lime is depleted, the pozzolanic reactions stops and the remaining
levels of silica remain inactive. Such an observation is further reinforced by the rate of the pozzolanic
reaction of SFA, which at high replacement levels (30%) drops bellow 0.5. That is the reason why at
these quantities of SFA, the strength and the service life in carbonation was reduced compared to
control.
In terms of environmental cost fly ash (in general) produced bigger reductions (28.7%) of the
associated CO2 emissions, compared to silica fume (14.5%). These reductions and the overall trends
observed in strength and service life were also observed on other mix designs investigated, with the
same content level of SCM (up to 30%) and initial cement content (300 kg/m3), but with different w/c
ratios (Fig. 3.5). Even at mix designs with different initial cement contents than control (from 300-400
kg/m3), with the same replacement level of SCM (up to 30%) and of 0.5 w/c ratio, the percentage
reductions in environmental cost was constant.
Taking under consideration that any further SCM addition would result in a bellow 1 (or even 0.5)
degree of pozzolanic reaction, in order to further reduce the environmental cost incremental cement
and water reductions took place (Step 4). Each reduction of cement content (by 10 kg/m3) is associated
with a reduction in environmental cost, while at the other hand, the water reduction (again by 10 kg/m3,
96
Chapteer 3 - PhD Disssertation
for each cement reduuction) enhannces the conccrete and serrvice life propperties (as illlustrated in Fig.
F 3.6).
It was shhown that the environmeental cost of a 30% CFA mix (reduced already byy 28.7 % com
mpared to
the conttrol mix) cann be furtherr reduced upp to 45%, with g/m3) and
w step by step cemennt (by 10 kg
additionaal water redductions. Succh a mix dessign, except the considerrable reduceed level of associated
a
CO2 emiissions, prodduces strengtth and servicce life (for ch
hloride expossure) values of more thaan 26.5 %
and 150 % above thee initial targeet values of 40
4 MPa and 50
5 years, resppectively.
Taking under
u consideration thee effects of each increm
mental cemeent and watter reduction
n on the
mental cost, strength (Fig. 3.8) and seervice life (F
associateed environm Fig. 3.9) propperties, in esssence an
area of accepted
a perrformance (inn terms of sttrength and service life) can be definned. On each Figure,
for each reduction inn cement conntent, apart of
o the decreaase in environnmental costt, the gain in
n strength
and servvice per wateer content reduction is allso illustrated
d, expressedd as a percenntage above the
t initial
set target values for strength
s (40 MPa) and seervice life (50
0 years).
100
5.8%
(W40)45
InitiallySetValue
75
Strength (%)>
(%) >
50
(40MPa)
25
(W10)12.3%
0
Reduction(%)in
Environmental
Cost
(%) in
25
Reduction
50
0 10
0 20 3
30
40 50 60
10kg/m33stepbystepdecreaseofiinitialCementContent(kg/m3)
W10
0 W20
0 W30
0 W40
0 Ecred
duction(%)
Figure 3.8
3 Effect off reduction off water and cement
c conteents on strenggth and enviironmental co
ost.
ment content of the 30% CFA mix byy 30 kg/m3, w

For a redduction of thhe initial cem we can achiev
ve a 38.2%
reductionn in environm
mental cost. At the samee time, the associated streength would bbe 12.3% hig
gher than
40 MPa for a 10 kg/m3 water redduction and 45.8
4 %, for a 40kg/m3 water
w reductioon (the corresponding
service life
l values would be 3.4%
% and more than
t 150% fo
or the same water
w reductiions).
97
J.G. Tapaali
200,0
(W40)>150%
ServiceLife(%)>Initially
Life (%) > Initially
150,0
SetValue(50years)
100,0
Service
50,0
0,0
Reduction(%)in
EnvironmentalCost
(W10)3.4%
R d ti (%) i
50,0
0 10 20 3
30 4
40 5
50 6
60
mentContent(kg/m3)
10kg//m3stepbysttepdecreaseofinitialCem
W10 W20 W30
W40 Ecred
duction(%) Zcl(%
%)>setvalue
Figure 3.9
3 Effect off reduction off water and cement
c conteents on servicce life and ennvironmenta
al cost.
Hence the designer can adjust the mix deesign configu

uration of a particular concrete miix design
incorporrating SCM, in achievingg further reduuction in env
vironmental cost
c (in addittion to those achieved
through clinker replaacement), annd at the sam
me time can select,
s for thiis particular cement redu
uction the
levels off required strrength and seervice life.
98
Chapter 4. Investigation on the effectiveness of biomass

ashes as supplementary cementing materials
4.1 Introduction
Portland cement is well recognized as the major construction material throughout the world. Given its
known environmental issues (in terms of energy and raw materials required for its production), direct
reduction of its clinker content through utilization of industrial by-products as supplementary
cementing materials (SCM), is a very promising first step in reducing considerably the associated
environmental burden (see Chapter 3). Just to reinforce this observation, it has been estimated
(Ecosmart Concrete 2008) that 18 % replacement of Portland cement would result in a 17 % reduction
of CO2 emissions and that, if just 30% of cement used globally were replaced with SCM, the rise in
CO2 emissions from cement production could be reversed.
Industrial by-products, such as blast furnace slag, fly ash and silica fume have been used as
traditionally supplementary cement replacement materials (both in the production of clinker and in
partial replacement of Portland cement in mortars and concrete) for the last 30 years. A number of
investigations have demonstrated the validity of using these materials from both technical,
environmental reasons and, at times, even economical (Papadakis et al. 2002, Antiohos et al. 2007,
Papadakis and Tsimas 2002). Today, research studies (Genesan et al. 2007, Frias et al. 2007,
Tangchirapat and Jaturapitakkul 2010, Sousa-Coutinho and Papadakis 2011) are indicating the
feasibility of using pozzolans originating from the agricultural industry, through biomass utilization.
Biomass in general, considered as one of the major renewable energy sources (in absolute terms),
accounts for more than 4% of the total energy consumption in the European Union (EU) (IEA 2011).
However, despite its wide use as energy source much of the waste produced remain unprocessed (Von
Bergs and Feuerborn 2005). Various types of biomass, from agro-industrial processes, produces ash
(as rice husk ash, palm oil fuel ash, sugar cane bagasse ash, etc.) which under certain conditions
99
J.G. Tapali
(chemical configuration, level of fineness) can have a similar pozzolanic activity to coal fly ash
(Genesan et al. 2007, Frias et al. 2007, Tangchirapat and Jaturapitakkul 2010, Sousa-Coutinho and
Papadakis 2011, Wang et al. 2008). These agro-waste ashes, containing a large amount of silica in
amorphous form, have potential for use as pozzolanic materials replacing cement (Rajamma et al.
2009).
Strict interpretation of ASTM C618 2012 (and of most standards in other countries addressing a
similar issue) precludes the use of any material (including biomass ash) not derived from coal
combustion, in cement and concrete utilization. The fraction of fly ash that qualifies under this strict
interpretation for use in concrete is in rapid decline due to issues such as co-firing fuels with coal and
injecting a variety of materials for emission control (Wang et al. 2008). This observation is essential,
due to the fact that biomass ash can be originated through a number of processes including pure solid
biomass combustion or co-firing (of a less than 10% biomass by energy content) with coal. In terms of
the latter, eventhough biomass co-firing is a way of producing cost effective and efficient renewable
power, the relatively low amounts of biomass in the co-firing process leads in general to low contents
of the biomass derived ash. Solid biomass combustion is a proven technology for heat and power
production, where the technologies of fluidized bed and grate furnace combustion are mainly used
(Loo and Koppejan 2003, Yin et al. 2008). The quantity and quality of ashes produced in a biomass
power plant are strongly influenced by the characteristics of the biomass used: agriculture wastes or
herbaceous biomass, wood or bark (Loo and Koppejan 2003, Masia et al. 2007). Combustion of wood,
for example, generates fewer amounts of ashes to be managed, because herbaceous biomass,
agriculture wastes and bark have higher ash content when compared to wood (Rajamma et al. 2009).
Biomass ashes differ from coal ashes, in terms of chemistry and mineralogy. The characteristics of
ashes from biomass combustion vary widely and are influenced by: (i) biomass characteristics (for
example, herbaceous material, wood or bark), (ii) combustion technology (for example, fixed bed or
fluidized bed), (iii) the location where the ashes are collected (for example, bottom ashes or fly ashes)
(Loo and Koppejan 2003, Yin et al. 2008, Obernberger et al. 1997). Typically, fly ash from neat
biomass combustion has more alkali (Na and K) and less alumina (Al2O3) than coal fly ash (Llorente
and Garcia 2006, Thy et al. 2006).
Most of the biomass ash produced in thermal power plants is either disposed of in landfill or recycled
on agricultural fields or forest (Loo and Koppejan 2003). Considering that the disposal cost of biomass
ashes and biomass ash volumes are increasing (worldwide), a sustainable ash management has to be
established. In addition, exploitation by the cement/concrete industry of agro-industrial ashes can be
an attractive activity for several countries which use great volumes of rice husk, palm oil fuels and
sugar cane bagasse as biomass in processes of energy cogeneration (such as China, India, Brazil and
Thailand).
100
Considerable amount of work on developing analytical models for the evaluation of (traditional) SCM
in concrete using the concept of efficiency factors (or k-values, to compare the relative performance of
supplementary cementing materials on concrete durability, Papadakis et al. 2002, Antiohos et al. 2007,
Papadakis and Tsimas 2002) has identified the high-added value of certain types of these materials and
their pozzolanic properties on cement and mortar and the effects they entail on early concrete strength
and volume stability (Papadakis 1999a, Papadakis 1999b, Papadakis and Demis 2013).
The same principle can be applied to biomass ashes, as presented in this chapter. By selecting data
from representative biomass ashes from the literature, the feasibility of their utilization in cement
manufacturing, as pozzolanic materials is investigated. An evaluation of the ashes in terms of the
derived efficiency factors for 28 days compressive strength (as calculated based on the analytical
models of strength prediction developed and validated elsewhere; Papadakis and Demis 2013), further
enhanced by their performance in chloride penetration (as defined in ASTM C 1202 2012) is presented
in this study. The main aim is to try to shed some light on the specific influence of the main
characteristics of biomass ashes on concrete strength development and performance in chloride
exposure, exploring in this way their future utilization in cement and concrete manufacturing.
4.2 Types and evaluation methodology for biomass ashes
4.2.1 Types of biomass ashes investigated
Based on data from the literature, a range of characteristic types of biomass (and other) ashes was
selected, including rice husk ash and mixtures (RHA), palm oil fuel ash (POFA), sugar cane bagasse
ashes (SCBA) and wood ashes (WA). Their origin and main points concerning their chemical
composition is briefly discussed bellow and presented in Table 4.1.
Rice husk ash (RHA), an agricultural waste material, produced by controlled burning of rice husk has
shown to contain highly reactive silica which could contribute chemically to Portland cement
ingredients. Typical highly reactive RHA ashes (Hwang et al. 2011, Saraswathy and Song 2007,
Ganesan et al. 2008) with SiO2 content of more than 90% were selected. Their reactivity is attributed
to the high content of amorphous silica, and to the very large surface area governed by the porous
structure of the particles. Generally, the reactivity is also favored by increasing the fineness of the
RHA (expressed in this study as the median size d50 in m). In addition certain RHA mixtures, utilizing
eucalyptus bark (RHBA) and chop wood (BRWA) were also selected. Rice huskbark ash (Chalee et al.
2013) is a by-product produced from burning a mixture of rice husk (65%) and eucalyptus bark (35%)
101
J.G. Tapali
by fluidized bed combustion process in a biomass power plant (used as fuel). The level of SiO2 (of
more than 74%) indicates a high potential for pozzolanic reactivity. According to ASTM C 618, this
particular type of biomass ash can be said to be Class N pozzolan since the sum of SiO2, Al2O3, and
Fe2O3 are higher than or close to 70%, SO3 content is not higher than 4%, and loss of ignition (LOI) is
close to 10%.
Table 4.1 Chemical composition and characterization of biomass ashes.
SiO2 Al2O3 Fe2O3 CaO SO3 Na2O3 K2O d50 Density

Type LOI *
(%) (%) (%) (%) (%) (%) (%) (m) (kg/m3)
Rice GRHBA 1
87.0 1.08 2.58 1.25 0.09 0.08 1.0 5.71 10.8 2150 k
Husk GRHBA2 74.8 0.20 0.80 5.90 0.50 0.20 2.0 11.2 10.8 2150 k
Ash BRWA3 78.4 2.60 1.70 7.40 1.10 0.20 3.7 3.60 15.5 2100 k
RHA4 91.0 0.35 0.41 1.95 1.21 0.08 3.21 8.50 12.0 2060 k
k,
RHA5 87.3 0.22 0.28 0.48 - 1.02 3.14 2.10 3.80 2060 RCPT-
RHA6 92.9 0.31 0.26 0.53 - 0.08 2.06 1.97 - - RCPT
RHA7 91.6 0.35 0.40 0.60 - 0.30 1.60 3.70 7.41 2050 RCPT
Palm GPOFA8 65.3 2.50 1.90 6.40 0.40 0.30 5.70 10.0 19.9 2170 k
Oil GPOFA9 65.3 2.50 1.90 6.40 0.40 0.30 5.70 10.0 10.1 2330 k
Fuel GPOFA10 65.3 2.60 2.00 6.40 0.50 0.30 5.70 10.1 10.1 2330 k
Ash POFA11 55.5 9.20 5.60 12.4 2.30 - - 7.90 10.7 2530 k
POFA12 63.6 1.60 1.40 7.60 0.20 0.10 6.90 9.60 7.20 2250 RCPT
Sugar SCBA13 78.3 8.90 3.60 2.20 - 0.10 3.50 - 2.70 2530 k
Cane SCBA14 64.2 9.05 5.52 8.14 - 0.92 1.35 4.90 5.40 1850 k, RCPT
b. ash SCBA15 78.4 8.55 3.61 2.15 - 0.12 3.46 0.42 - 2530 k, RCPT-
Wood W(S)A16 31.8 28.0 2.64 10.5 0.45 6.50 10.4 27.0 - 2130 k
Ash HCWA 17
28.0 4.10 2.50 39.0 1.00 1.00 7.40 7.22 5.16 2520 k
1
GRHBA: Ground rice husk bark ash, 65% rice husk and 35% eucalyptus bark, Chalee et al. 2013
2
GRHBA: Ground rice husk bark ash, Sata et al. 2007
3
BRWA: Bagasse rice husk wood ash, 15% rice husk, 82.5% bagasse ash and 2.5% chop wood, Horsakulthai et
al. 2011
4
RHA: Rice husk ash, Hwang et al. 2011
5
RHA: Rice husk ash, Ganesan et al. 2008
6
RHA: Rice husk ash, Saraswathy and Song 2007
7
RHA: Rice husk ash, Chindaprasirt et al. 2008
8
GPOFA: Ground palm oil fuel ash, coarse ground, Tangchirapat and Jaturapitakkul 2010
9
GPOFA: Ground palm oil fuel ash, fine ground, Tangchirapat and Jaturapitakkul 2010
10
GPOFA: Ground palm oil fuel ash, Sata et al. 2007
11
POFA: Palm oil fuel ash, Tangchirapat et al. 2012
12
POFA: Palm oil fuel ash, Chindaprasirt et al. 2008
13
SCBA: Sugar cane bagasse ash, Cordeiro et al. 2012
14
SCBA: Sugar cane bagasse ash, Ganesan et al. 2007
15
SCBA: Sugar cane bagasse ash, Cordeiro et al. 2009
16
W(S)A: Wood (sawdust) ash, Abdullahi 2006
17
HCWA: High calcium wood ash, Chee and Mahyuddin 2012
*
Denotes if the particular type of ash was used for strength (k) of for Rapid Chloride Permeability Test (RCPT)
assessment
102
Bagasse-rice husk-wood ash (BRWA) (Horsakulthai et al. 2011) is a by-product obtained from biomass
power plants that use bagasse (82.5%), rice husk (15%) and chop wood (2.5%) co-burning in
producing steam for generating electricity to supply the sugar mills. It should be noted that most of the
BRWA is disposed of as waste in landfill which causes environmental problems such as air pollution as
well as groundwater quality problem owing to the leaching of metals from the ashes. In terms of
chemical composition, the sum of SiO2, Al2O3, and Fe2O3 was 82.7% and the LOI was 3.6% (< 10%)
complying with ASTM C618 requirement as a natural pozzolan.
Palm oil fuel ash (POFA) is a by-product of the palm oil industry. It is a waste obtained from burning
palm oil fibers, shells, and empty fruit bunches as fuel in producing steam to generate electricity for
the palm oil extraction process. In general, it contains high amounts of silicon and aluminum oxides
(in the amorphous state) and was recently accepted as a pozzolanic material (Tangchirapat and
Jaturapitakkul 2010). According to the chemical composition of the types of POFA selected in this
study (Tangchirapat and Jaturapitakkul 2010, Sata et al. 2007, Tangchirapat et al. 2012, Chindaprasirt
et al. 2008), of an average SiO2 composition from 55% to 65% and LOI in the region of 10%, it can be
said that, although POFA is not a natural pozzolan, it may be classified as Class N (natural) pozzolan
according to ASTM C618 2012.
Sugar Cane Bagasse Ash (SCBA) is a by-product of the industry involved with sugar cane and alcohol
production. The bagasse is usually burned in boilers at temperatures varying from 700 to 900 C.
Preliminary investigations on SCBA have demonstrated that it presents the appropriate chemical
composition for application as a pozzolan, mainly in regard to its high silica content and presence of
amorphous silica (Cordeiro et al. 2009). However, it is important to note that the SiO2 content (78.3%)
covers amorphous and crystalline silica (from SCBA) and some sand contamination has been
observed, identified by the presence of quartz and cristobalite phases in the diffraction patterns of
SCBA. This high content of quartz is ultimately due to sand adhered to the sugar cane, which is
harvested along with it. Even after washing the sugar cane, sand can represent as much as 2% in
weight of the material that is processed (Cordeiro et al. 2009). After the loss of organic matter during
bagasse burning, this proportion increases significantly. The presence of cristobalite, previously
mentioned, can be associated to the high temperature in the boiler.
Wood ash (WA) is the inorganic and organic residue generated due to combustion of wood and wood
products (chips, saw dust, bark, etc.). Typically wood burned for fuel at pulp/paper mills or at wood
products industries, consist of saw dust, wood chips, bark, saw mill scraps, hard chips rejected from
pulping and excess screenings sheaves (Abdullahi 2006). In a sense it can be related to fly ash since
fly ash is obtained from coal, which is a fossilized wood. The chemical composition of the selected
types of WA indicates very high LOI, high alkali content and very low SiO2 values. Overall, these
103
J.G. Tapali
particular types of WA do not satisfy the requirements prescribed in ASTM Standard C618 to be
classified as a Class N pozzolan. It should also be noted that the high loss of ignition means that the
wood ash contains appreciable amount of un-burnt carbon which reduces its pozzolanic activity. The
un-burnt carbon is not pozzolanic and its presence serves as filler to the mixture.
4.2.2 Methodology followed for the evaluation of biomass ashes as cementitious materials
According to the chemical configuration of these types of ashes, the mix design (w/c ratio, cement
content, SCM replacement level, aggregate size) used in each particular study and based on the
compressive strength data available from the literature (noted as experimental), estimation of the
compressive strength for a range of k-values, took place. Such calculations were possible using an
analytical tool for the estimation of concrete strength and service life; EUCON; Papadakis and
Efstathiou 2005. For each type of biomass ash used in this study, different sets of compressive strength
data were estimated for a range of k-values (from the very low value of 0.2 to higher values of 1.7).
Each set of strength data, was evaluated in terms of statistical proximity to the experimental strength
values, based on the principles of the least squares method (Table 4.2, Figure 4.1). The k-value of the
set of data that provided the best fit was assumed to be the efficiency factor (for 28 days compressive
strength) of the biomass ash.
In addition, where data were available, the performance of biomass ashes in terms of chloride ion
penetration, expressed as the total charge passed through biomass ash blended concrete specimens
(measured according to ASTM C 1202), were evaluated. Based on the values of charge (Coulombs)
passed through each individual biomass ash concrete investigated, with increasing SCM content, the
difference (%) to control (no SCM addition) was calculated, as it is illustrated in Section 4.3.2 of this
study.
Table 4.2 Regression analysis for the calculation of k-value of ashes based on the estimation of
compressive strength (representative example for Ground Rice Husk Bark Ash, Sata et al.
2007).
Calculated Compressive Strength (MPa)

SCM Experimental
k factor for 28 days compressive strength
compressive strength (MPa)
Type (%) 1.0 1.2 1.4 1.6
GRHBA 0 78 80.1 80.1 80.1 80.1
10 86 80.1 81.8 83.4 85.0
20 88 80.3 83.6 86.7 89.9
30 85 71.0 74.0 77.1 82.0
SLSQ 294.5 162.4 75.3 18.0
104
100 100

80 80
xi
60 60
40 min (xi)2 denotes the best fitting 40

of the experimental to
20 the caluclated strength 20
(a) values (b) POFA
0 0
0 10 20 30 40 0 10 20 30 40
SCM Content (%) SCM Content (%)
100 100
Compressive Strnegth (MPa)
(d) WA
80 80
60 60
40 40
20 20
(c) SCBA
0 0
0 10 20 30 40 0 20 40 60
SCM Content (%) SCM Content (%)
Figure 4.1 Estimation of k-factor using regression analysis, (a) schematic overview, and typical
examples (b) POFA, Sata et al. 2007, (c) SCBA, Ganesan et al. 2007, and (d) WA,
Abdullahi 2006.
4.3 Results of biomass ashes evaluation
In terms of compressive strength development it should be noted that, a common observation from the
literature (as indicated in Figure 4.1) is that there is an optimum level of cement replacement by
biomass ashes. After a certain percentage of biomass ash, the derived strength values are reducing (in
some cases being higher than control). This can be attributed to the initial fast rate of the pozzolanic
reaction, which at high replacement levels this rate drops at values bellow one and the filler effect
becomes more pronounced.
105
J.G. Tapali
Overall, in most of the RHA mixtures the high levels of amorphous silica and the fine particle size of
RHA are the principle reasons for the excellent pozzolanic activity and the increase in compressive
strength observed.
Utilisation of Palm oil fuel ashes (with SiO2 content on average in the region of 65%, less than that of
the RHA types of ashes) in the concrete mix contributed to the compressive strength, via a fast
pozzolanic reaction, depending on the level of fineness of the POFA. The compressive strength of
concrete with 20% POFA (Sata et al. 2009) was found to be higher than those of 10% and 30%
(Figure 4.1b). At another study (Tangchirapat and Jaturapitakkul 2010) for the same percentage of
POFA (20%) of the same chemical composition but of different level of fineness (of median size 19.9
m and 10.1 m) the one with the lower median size resulted in higher compressive strength (33 MPa,
for d50 of 10.1 m, compared to 27 MPa for d50 of 19.1 m) at 28 days.
The same was noticed on SCBA mixes (Ganesan et al. 2007). Up to 20% replacement level the
compressive strength was higher compared to control specimens, while at higher levels the strength
was decreased.
As far as WA is concerned, results from the literature (Abdullahi 2006, Chee and Mahyuddin 2012)
showed in general the increase in the levels of cement replacement resulted in a gradual decrease in
the compressive strength. Despite the subsequent strength reduction per increasing level of WA
incorporation, the mix containing 20% wood ash had higher strength than that containing 10% wood
ash at 28 days. This was due to the fact that the silica provided by 10% wood ash was inadequate to
react with the calcium hydroxide produced by the hydration of cement. Increase in wood ash content
beyond 20% resulted in a reduction in strength. In this case the silica present in the mix was in excess
of the amount required to combine with the calcium hydroxide from the hydrating cement. The excess
silica had no pozzolanic value but only served as filler.
4.3.1 Efficiency factors
An overview of the calculated k-factors, per group category of the biomass ashes investigated, is
illustrated in Figure 4.2 and given Table 4.3. A first observation is that the different origins and
chemical configurations of the individual ashes resulted in different k-values. Overall, on average, a k-
value of 1.38 was calculated for rice husk (and mixtures) ashes, while for palm oil fuel and sugar cane
bagasse ashes the corresponding efficiency factors were found to be 1.2 and 0.5 (respectively). As it
was expected wood contained ashes gave k-values bellow 0.2.
106
Chapteer 4 - PhD Diissertation
Figure 4.2
4 Estimatiion of k-values of variouss biomass ashes.
Table 4..3 k-valuess of ashes invvestigated inn this study.
SCM SiO2 Al2O3

A Fe2O3 1+2 11+2+3 O
CaO SO3 N 2O3
Na K 2O LOI d50
k
Type (%) (%) (%)) (%) (%) (%) (%) (%) (%) (%) (
m)
GRHBA 87.0 1.08 2.588 88.1 90.7 1.25 0.09 0.08 1.000 5.71 10.8
1 1.5
GRHBA 74.8 0.20 0.800 75.0 75.8 5.90 0.50 0.20 2.000 11.2 10.8
1 1.6
RHA 91.0 0.35 0.41 91.3 91.8 1.95 1.21 0.08 3.211 8.50 12.0
1 1.3
RHA 87.3 0.22 0.288 87.5 87.8 0.48 - 1.02 3.144 2.10 3.80
3 1.5
BRWA 78.4 2.60 1.700 81.0 82.7 7.40 1.10 0.20 3.700 3.60 15.5
1 1.0
GPOFA 65.3 2.50 1.900 67.8 69.7 6.40 0.40 0.30 5.700 10.0 10.1
1 1.5
GPOFA 65.3 2.50 1.900 67.8 69.7 6.40 0.40 0.30 5.700 10.0 19.1
1 1.2
GPOFA 65.3 2.60 2.000 67.9 69.9 6.40 0.50 0.30 5.700 10.1 10.1
1 1.3
POFA 55.5 9.20 5.600 64.7 70.3 12.4
4 2.30 - - 7.90 10.7
1 1.0
SCBA 64.2 9.05 5.522 73.2 78.7 8.14

4 - 0.92 1.355 4.90 5.40
5 0.8
SCBA 78.3 8.55 3.61 86.9 90.5 2.15 - 0.12 3.466 0.42 - 0.4
SCBA 78.3 8.90 3.600 87.2 90.8 2.20 - 0.10 3.500 - 2.70
2 0.5
W(S)A 31.8 28.0 2.644 59.8 62.1 10.5 0.45 6.50 10.44 27.0 - 0.2
HCWA 28.0 4.10 2.500 32.1 34.6 39.0 1.00 1.00 7.400 7.22 5.16
5 0.15
107
J.G. Tapali
In particular the following main observations can be made:
RHA and mixtures (rich in rice husk ash) produced k-values of above 1.3, up to 1.6 (except
BRWA, Horsakulthai et al. 2011, with a RHA participation of 15%, which gave a k-value of 1.0).
The low level of fineness (expressed as d50) from 3.8 m to 10.8 m, does not seem to have a
profound effect on the derived k-factors, since RHA of similar compositions produced values of 1.5
to 1.6. However, for a median size of 12 m, the derived efficiency factor was slightly lower (1.3).
These inconsistencies with the level of fineness were also observed in the case of sugar cane
bagasse ash (SCBA), but for similar (low) d50 values. A particular type of SCBA with a d50 of 2.70
m, produced a k-value of 0.5 (Cordeiro et al. 2012), while a similar type of SCBA with larger d50
value of 5.4 m, produced a k-value of 0.8 (Ganesan et al. 2007). This difference however can be
attributed on the fact that the SCBA with the low k-value was rich in crystalline silica.
Palm oil fuel ashes (POFA) with less SiO2 content than RHA produced in certain cases similar k-
factors (1.3; Sata et al. 2007, 1.5; Tangchirapat and Jaturapitakkul 2010).
The level of fineness appears to have some effect on POFA mixtures (Tangchirapat and
Jaturapitakkul 2010, Sata et al. 2007, Tangchirapat et al. 2012). For the same chemical
composition of POFA reduction of the d50 from 19.1 m to 10.1 m (Tangchirapat and
Jaturapitakkul 2010) was translated as an increase of the k-values (from 1.2 to 1.5). However,
another type of POFA with a similar level of fineness to 10.1 m (10.7 m) (Tangchirapat et al.
2012) produced a k-value of 1.0 (much lower than 1.5).
4.3.2 Chloride penetration
As it was previously mentioned, where data were available, the performance of biomass ashes in terms
of chloride ion penetration, (measured according to ASTM C 1202), was evaluated. The difference
(%) to control (no SCM addition) in terms of charge passed per increasing SCM content is given in
Table 4.4 and Fig. 4.3.
Overall, the charge passed was substantially reduced with incorporation of biomass ashes into the
concrete mix. Cement replacement by rice husk ash drastically reduced the (per ASTM C1202) rapid
chloride penetrability of concrete from a low (charge ranging from 1000 to 2000 C) to very low
(charge ranging from 100 to 1000 C) ratings (per ASTM C1202). In general RHA was found to be
more drastic in that sense, than SCBA and POFA. Incorporation of 20% RHA (Figure 4.3a) produced
a reduction in the charge passed of more than 60% (and up to 90%), while at lower biomass ash
quantities (10%) a steady reduction (for all RHA investigated) of 43% on average was noticed.
108
Chapteer 4 - PhD Diissertation
Table 4..4 Perform

mance in RCP
PT in terms of
o reduction in
i electrical charge
c passeed.
SCM SCBA [5] SCBA

A [32] R
RHA [25] RHA [31] RHA [26] PO
OFA [31]
(%) (C) D(%%) (C) D(%) (C
C) D(%) (C) D(%%) (C) D(%) (C)) D(%)
0 2780 0 1179 0 1161 0 7450 0 2870 0 745
50 0
5 2045 26.4 783 33.6 1108 4.57 - - 2200 23.3 - -
10 1850 33.5 774 34.4 6553 43.8 - - 1500 47.7 - -
15 1300 53.3 882 25.2 3009 73.4 - - 1250 56.5 - -
20 1200 56.8 - - 2665 77.2 750 89..9 1000 65.2 195
50 73.8
25 1050 62.2 - - 2113 81.7 - - 850 70.4 - -
30 2090 24.8 - - 2773 76.5 - - 780 72.8 - -
35 - - - - - - - - 950 66.9 - -
40 - - - - - - 250 96..6 - - 100
00 86.6
(C) Chargge passed (in Coulombs),
C (D
D) Differencee to the contro
ol value (%)
charge rannging from 10000 to 2000 C:
C low permeabbility, while from
f 100 to 10000 C: very loow permeabiliity
RHA RHA A RHA

(a) [25] [31]] [26]
SiO2 (%) 992.9 91.6 87.3
Al2O3 (%) 00.31 0.35 0.22
Fe2O3 (%) 00.26 0.40 0.28
CaO (%) 00.53 0.60 0.48
SO3 (%) - - -
LOI (%) 1.97 3.70 2.10
d50 (m) - 7.41 3.80
S
SCBA SCBAA POFA
(
(b) [5] [32] [31]
SiO2 (%) 64.2 78.44 63.6
Al2O3 (%) 9.05 8.555 1.60
Fe2O3 (%) 5.52 3.611 1.40
CaO (%) 8.14 2.155 7.60
SO3 (%) - - 0.20
LOI (%) 4.90 0.422 9.60
d50 (m) 5.40 - 7.20
Figure 4.3
4 Perform
mance of reprresentative biomass ashess in RCPT.
109
J.G. Tapali
4.4 Discussion
Trying to identify the specific influence of the main characteristics of the biomass ashes on the
efficiency factors, it can be noted that:
overall RHAs, rich in SiO2 content (> 85%), produced high k-values,
wood containing ashes, with very low SiO2 content (< 30%), produced the lowest k-values.
Hence, it appears that the influence of SiO2 should be quite significant on the derived k-value of the
ash. However, considering that SCBA with higher SiO2 content than that of POFA produced smaller
k-values than the latter type of ash, the influence of SiO2 content is not straight forward.
In the literature (Papadakis et al. 2002, Papadakis and Tsimas 2002, Lothenbach et al. 2012) there is a
consensus that the activity of SCMs, in general (including biomass ashes), is mainly attributed to the
fact that they possess significant contents of active constituents (active silica) that combine with
Ca(OH)2 produced from cement hydration to form hydration products with binding properties. It is the
active silica (non-crystalline silica glass, present in the amorphous and mostly vitreous part of the
SCM), which is part of the total silica content of the SCM that is involved in the hydration reactions
producing CSH to which the strengthening of cement is attributed. However, for the variety of
biomass ashes investigated in this study, information on the active silica content was unavailable. On
this note, benchmarking of the different types of ashes used in this project in terms of the influence of
SiO2 content and of the added influence of SiO2 with the other primary oxides (Al2O3, Fe2O3), on the
derived efficiency factors, is given in Table 4.5 and illustrated in Figure 4.4.
Although a trend, that with reducing SiO2 content smaller derived k-values are derived, is slightly
evident (Figure 4.4a), certain abnormalities (points 4, 5, 6 and 11 illustrated in Figure 4.4a and
highlighted in Table 4.5a) distort this image.
A closer look reveals that ashes with high SiO2 content and low (up to 2.6 %) Al2O3 and Fe2O3
contents produced higher than 1.0 k-values. On the other hand ashes with high Al2O3 (more than 8%)
and Fe2O3 (above 2.6%) even if they are rich in SiO2 (78%), they produced k-values bellow 0.8. The
previously mentioned abnormalities refer to such types of ashes, namely sugar cane bagasse ashes;
points 5 (Abdullahi 2006), 6 (Cordeiro et al. 2012), 11 (Ganesan et al. 2007) in Figure 4.4a.
110
Table 4.5 Biomass ash results categorized by primary oxide contents; [a] SiO2 (%), [b] SiO2+Al2O3
(%) and [c] SiO2+Al2O3+Fe2O3 (%) contents.
Eq.
SCM SiO2 Al2O3 Fe2O3 Si+Al Si+Al+Fe CaO SO3 LOI d50
a/a Alk. k
Type (%) (%) (%) (%) (%) (%) (%) (%) (m)
(%)
1 GRHA 91.0 0.35 0.41 91.4 91.8 1.95 1.21 2.19 8.50 12.0 1.3
[a] 2 RHA 87.3 0.22 0.28 87.5 87.8 0.48 - 3.09 2.10 3.80 1.5
3 GRHBA 87.0 1.08 2.58 88.1 90.7 1.25 0.09 0.74 5.71 10.8 1.5
4 BRWA 78.4 2.60 1.70 81.0 82.7 7.40 1.10 2.63 3.60 15.5 1
5 SCBA 78.3 8.55 3.61 86.9 90.5 2.15 - 2.40 0.42 - 0.4
6 SCBA 78.3 8.90 3.60 87.2 90.8 8.14 - 1.81 4.90 5.40 0.5
7 GRHBA 74.8 0.20 0.80 75.0 75.8 5.90 0.50 1.52 11.2 10.8 1.6
8 GPOFA 65.3 2.60 2.00 67.9 69.9 6.40 0.50 4.05 10.1 10.1 1.3
9 GPOFA 65.3 2.50 1.90 67.8 69.7 6.40 0.40 4.05 10.0 10.1 1.5
10 GPOFA 65.3 2.50 1.90 67.8 69.7 6.40 0.40 4.05 10.0 19.1 1.2
11 SCBA 64.1 9.05 5.52 73.2 78.7 8.14 - 1.81 4.90 5.40 0.8
12 POFA 55.5 9.20 5.60 64.7 70.3 12.40 2.30 0.00 7.90 10.7 1
13 WA 31.8 28.0 2.34 59.8 62.1 10.53 0.45 13.3 27.0 - 0.2
14 HCWA 28.0 4.10 2.50 32.1 34.6 39.0 1.00 5.87 7.22 5.16 0.15
1 GRHA 91.0 0.35 0.41 91.4 91.8 1.95 1.21 2.19 8.50 12.0 1.3
[b] 2 GRHBA 87.0 1.08 2.58 88.1 90.7 1.25 0.09 0.74 5.71 10.8 1.5
3 RHA 87.3 0.22 0.28 87.5 87.8 0.48 - 3.09 2.10 3.80 1.5
4 SCBA 78.3 8.90 3.60 87.2 90.8 8.14 - 1.81 4.90 5.40 0.5
5 SCBA 78.3 8.55 3.61 86.9 90.5 2.15 - 2.40 0.42 - 0.4
6 BRWA 78.4 2.60 1.70 81.0 82.7 7.40 1.10 2.63 3.60 15.5 1
7 GRHBA 74.8 0.20 0.80 75.0 75.8 5.90 0.50 1.52 11.2 10.8 1.6
8 SCBA 64.2 9.05 5.52 73.2 78.7 8.14 - 1.81 4.90 5.40 0.8
9 GPOFA 65.3 2.60 2.00 67.9 69.9 6.40 0.50 4.05 10.1 10.1 1.3
10 GPOFA 65.3 2.50 1.90 67.8 69.7 6.40 0.40 4.05 10.0 10.1 1.5
11 GPOFA 65.3 2.50 1.90 67.8 69.7 6.40 0.40 4.05 10.0 19.1 1.2
12 POFA 55.5 9.20 5.60 64.7 70.3 12.4 2.30 0.00 7.90 10.7 1
13 WA 31.8 28.0 2.34 59.8 62.1 10.5 0.45 13.3 27.0 - 0.2
14 HCWA 28.0 4.10 2.50 32.1 34.6 39.0 1.00 5.87 7.22 5.16 0.15
1 GRHA 91.0 0.35 0.41 91.8 91.4 1.95 1.21 2.19 8.50 12.0 1.3
[c] 2 SCBA 78.3 8.90 3.60 90.8 87.2 8.14 - 1.81 4.90 5.40 0.5
3 GRHBA 87.0 1.08 2.58 90.7 88.1 1.25 0.09 0.74 5.71 10.8 1.5
4 SCBA 78.3 8.55 3.61 90.5 86.9 2.15 - 2.40 0.42 - 0.4
5 RHA 87.3 0.22 0.28 87.8 87.5 0.48 - 3.09 2.10 3.80 1.5
6 BRWA 78.4 2.60 1.70 82.7 81.0 7.40 1.10 2.63 3.60 15.5 1
7 SCBA 64.2 9.05 5.52 78.7 73.2 8.14 - 1.81 4.90 5.40 0.8
8 GRHBA 74.8 0.20 0.80 75.8 75.0 5.90 0.50 1.52 11.2 10.8 1.6
9 POFA 55.5 9.20 5.60 70.3 64.7 12.4 2.30 0.00 7.90 10.7 1
10 GPOFA 65.3 2.60 2.00 69.9 67.9 6.40 0.50 4.05 10.1 10.1 1.3
11 GPOFA 65.3 2.50 1.90 69.7 67.8 6.40 0.40 4.05 10.0 10.1 1.5
12 GPOFA 65.3 2.50 1.90 69.7 67.8 6.40 0.40 4.05 10.0 19.1 1.2
13 WA 31.8 28.0 2.34 62.1 59.8 10.5 0.45 13.33 27.0 - 0.2
14 HCWA 28.0 4.10 2.50 34.6 32.1 39.0 1.00 5.87 7.22 5.16 0.15
111
J.G. Tapaali
1,8 1,8
1,6 1,6
1,4 1,4
1,2 1,2
k-value
k-value
1 1
0,8 6 0,8 6 9
0,6 8 0,6 7
4
0,4 0,4 2
0,2 5 Wood Wood
[b] 0,2 [c] 4
ashes ashes
0 0
91,35
88,08
87,54
87,2
86,89
81
75
73,2
67,9
67,8
67,8
64,7
59 8
59,8
32,1
91,76
90,8
90 66
87,82
90,66
90,5
82,7
78,72
75,8
70,3
69,9
69,7
69,7
62,14
34,6
SiO2+Al2O3 (%) SiO2+Al2O3+Fe
+ 2O3 (%)
Figure 4.4
4 Effect of
o primary oxide
o contennts on k-va
alues of biomass ashes;; [a] SiO2 (%), [b]
SiO2+All2O3 (%) andd [c] SiO2+A
Al2O3+Fe2O3 (%) content.
In additiion to the abbove, two fuurther pointss strike out. A type of POFA
P (Tanggchirapat et al.
a 2012)
(point 122) with high Al2O3 and Fe
F 2O3 contentts but also ricch in CaO (112.4%) and a mixture typ
pe of ash,
BRWA (Horsakulthaai et al. 20111) (point 4) containing a very small portion (15%
%) of rice hu
usk wood
ash, beinng low in Al2O3 and Fe2O3 contents buut high in CaaO (7.4%).
Hence thhe influence of the level of SiO2 in thhe ash does carry certainn validity onn the derived
d value of
the efficciency factor, but is also affected by the composiition of the ash
a in other oxides. On that
t note,
the influuence of SiO
O2 in connecction to the other majorr oxides (Al2O3 and Fe2O3) is exam
mined. By
investigaating the com
mbined effecct of SiO2+A
Al2O3 contentt, a similar behavior is obbserved (Tab
ble 4.5bc,
Figure 4.4b,
4 c). The same trend//mishaps is observed
o as in
i the case of
o the effect of SiO2 conttent, with
the samee types of asshes and theiir particulariities as previiously explaiined (in prim
mary oxides and CaO
112
composition) deviating to a great extend. Such a deviation becomes even clearer when the combined
effect of all three major oxides on the derived k-values is investigated (Table 4.5c, Figure 4.4c).
A common observation of all of the above mentioned ash classifications (in terms of their primary
oxide contents) is that certain types of rice husk ash by producing high k-values, appear at the top of
these classifications, while, wood containing type of ashes (WA; Abdullahi 2006, HCWA; Chee and
Mahyuddin 2012), with very low derived efficiency factors (< 0.2), appear at the bottom. This is not
surprising since wood ashes, usually have very low contents in SiO2 and contain appreciable amounts
of un-burnt carbon (up to 27% in a particular WA, Abdullahi 2006, investigated in this study) which
reduces their pozzolanic activity to a great extend. Unburned carbon is not pozzolanic and its presence
serves as filler to the mixture causing however problems of volume stability. High unburned carbon
contents, the main form of LOI (loss on ignition) in the ash, are known to be responsible for strength
development and durability associated problems (increased water demand, increased permeability;
Hwang et al. 2011, Cordeiro et al. 2012, Wang and Baxter 2007).
It should be noted at this stage, that when the ash is produced in industrial combustion systems (as the
majority of the ashes investigated in this study), the temperature of combustion, the cleanliness of the
biomass fuel and the technology used can have profound effects on the characteristics of the ash,
especially on the unburned carbon content. Controlled burning at 800 C, through a fluidized bed
combustion process resulted in considerably higher values of LOI, compared to burning at 1300 C
(Sata et al. 2007). However, it has also been reported that smaller LOI values (or residual carbon
contents) of up to 12%, exhibited by every type of biomass ash investigated in this study, except wood
ash, did not have any detrimental effect on the strength and microstructure of cement and concrete
(Hornain et al. 1992).
Overall, at this point, it can be concluded that upon a certain percentage in Al2O3, Fe2O3 and CaO
contents, high SiO2 content translates into a high k-value. However, at high compositions of CaO
(even for low Al2O3, Fe2O3 contents) and/or at high contents of Al2O3, Fe2O3, the derived k-values are
not linear with that high SiO2 content. The way Al2O3, Fe2O3 and CaO contents influence the level of
the derived k-value, (even for a high contained percentage of SiO2 in the ash) is evident into the
following Figure 4.5.
On the range of biomass ashes investigated in this study, of similar particle median size (d50) and LOI,
concentration in Al2O3 of more than 4.1% produced efficiency factors bellow 1.0, even for high SiO2
content (more than 78%), as it illustrated at points 1 (Cordeiro et al. 2009) and 2 (Cordeiro et al. 2012)
in Figure 4.5a. In terms of Fe2O3 (Figure 4.5b) and CaO (Figure 4.5c) contents, concentration of more
than 3.0 % and 8.0 % respectively, produced efficiency factors well bellow 1.0. Overall, based on their
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J.G. Tapali
combined influence, it appears that as their percentages in the ash increase, the derived k-values drop
bellow 1.0, well even bellow 0.5 (Figure 4.5d).
Figure 4.5 Effect of high quantities of Al2O3 (%) [a], Fe2O3 (%) [b] and CaO (%) [c] contents on k-
values of ashes.
In terms of the influence of CaO results are contradictory. In theory, high CaO contents in the ash are
expected to contribute to hydraulic activity (Rajamma 2011). The pozzolanic activity of the ash in a
cement matrix enhances the formation of C-S-H gel, through the reaction of amorphous silica content
of the ash with the free lime from cement hydration. On that note, high CaO contents have been found
to further aid this particular process by reacting with the SiO2 content of the ash (Ganesan et al. 2007).
However, it has been reported that high carbon contents led to increased water demand of the concrete
mix (Hwang et al. 2011, Sata et al. 2007).
Although, relatively high alumina contents (and iron oxide) in cement in the form of C3A (3 CaO
Al2O3) or C4AF (4 CaO Al2O3 Fe2O3) phases, are known for their small contribution to early
114
strength development, their influence in the chloride binding capacity of the cement mix is crucial.
High alumina contents can increase cements potential for Friedels salt production. The latter is
formed as a result of the chloride binding by cementitious components (C3A, C4AF phases). This
process is beneficial, as far as the permeability of chlorides is concerned, since formation of Friedels
salt results in a less porous structure, hence to reduced transport of chlorides into the concrete mix.
Such a less porous structure, was observed on a variety of the biomass ashes (RHA, POFA and in
some SCBA) investigated in this study, based on the change of the reduction of chloride permeability
from low to very low rating (according to ASTM C1202), as it was discussed in the previous
section. Rapid Chloride Permeability Test (RCPT) indicated that the total charge passed on biomass
ash concrete samples, was considerably reduced (compared to control samples), up to almost 90% (as
it was indicated in Figure 4.3) for a 20% replacement by RHA. Considerable reductions were also
noticed for other types of biomass ashes (73.8 % for 20% POFA incorporation and 56.8 % for SCBA).
In general, the transport of chloride ions (and the consequent electrochemical processes) through
biomass ash blended concretes depends on the pore structure of the concrete, while the electrical
conduction depends on both pore structure characteristics and electrical conductivity of the pore
solution (Ganesan et al. 2008). Overall, the finer particles of ashes develop discontinuous and tortuous
pore in concrete structure and the pores present in the concrete are completely filled up by finer
particles.
Since the total charge passed through the concrete depends on the electrical conductance, low unburnt
carbon content present in some types of biomass ashes is known to contribute to the significant
reduction in the electrical charge passed. In general, a reduction in the unburnt carbon content may be
beneficial from the chloride permeability point of view. For example, when rice husk ash which has a
lower loss on ignition value compared to OPC is used to partially replace OPC, resistance to chloride
permeation is substantially improved. This may be probably due to a decrease in electrical
conductivity of concrete due to lowering of unburnt carbon content in RHA, in addition to pore
structure refinement and conductivity of pore solution. Such an observation is further reinforced
considering the substantial reductions in charge passed achieved when RHA was utilized (Figure 4.3)
with low LOI values from 1.97% to 3.7%.
Overall, the chloride-ion penetration results suggest pore refinement due to the pozzolanic reaction of
ultrafine biomass ash and demonstrate the significant potential of these types of ashes as mineral
admixtures in concrete, as long as an appropriate grinding strategy is used and product fineness is
achieved.
115
J.G. Tapali
116
Chapter 5. Utilization of rice husk ash in the building sector

Technoeconomical analysis and environmental
benefits
5.1 Introduction
5.1.1 General
Rice husk ash (RHA) is the solid-state residue of the incineration of the rice husk, a process used in the
rice industry for heat, steam and/or electrical power production. The potential uses of this by-product
include materials of high-added value like cement/concrete-production enhancing materials (pozzolanic
materials), zeolites, waterglass, etc. In the previous Chapter 4 it was observed that RHA can act as an
efficient pozzolanic material (and supplementary cementing material - SCM) provided its amorphous and
fine state and offering thus high environmental benefits to the construction industry.
RHA has shown to contain significant amount of reactive silica that could contribute chemically to the
development of pozzolanic reactions. In many cases depending on the nature of husks and
burning/cooling conditions the total silica of RHA exceeds 90% with most of it being non-crystalline,
thus reactive under alkaline conditions (Antiohos et al. 2014). Pozzolanic activity of RHA depends on
silica content, silica crystallization phase, and size and surface area of ash particles. Ideally, ash must
contain limited amount of unburnt carbon. RHA that has amorphous silica content and large surface area
can be produced by combustion of rice husk at controlled temperature (Mehta 1989) and these factors are
mainly responsible for its high reactivity (Mehta 1994, Sousa-Coutinho, 2003).
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J.G. Tapali
Reactivity of RHA is attributed to its high content of non-crystalline silica, and to its very large surface
area governed by the cellular structure of the particles as well (Mehta 1994, Zhang and Malhotra 1996,
Chandra 1997, Sousa-Coutinho 2003, Saraswathy 2007). When pozzolanic materials are added to cement,
the silica (SiO2) present in these materials reacts with free lime released during the hydration of cement
and forms additional calcium silicate hydrates (C-S-H) as new hydration products which improve the
mechanical properties of concrete formulation (Ganesan and Thangavel 2007).
Despite the fact that a lot of work has been done on treated RHA, results on the direct use of untreated
RHA are scarce in the literature and are usually limited to strength contribution and not durability aspects.
Feng et al. (2004), for example, examined the pozzolanic properties of both untreated and treated RHA
but did not attempt to assess their behavior in terms of durability. Sensale (2010) analyzed the effect of
two types of RHA (amorphous and partially crystalline optimized by dry-milling) on durability of
cementitious materials by proper testing. Other relevant studies (Gastaldini et al. 2009, Ramezanianpour
et al. 2009) have also examined the influence of untreated RHA in certain durability properties; however,
more investigation has to be conducted concerning its valorization in cement-based mortars and concrete
systems and especially properties like resistivity and resistance to carbonation.
Especially, RHA for building applications has great technical & environmental benefits, as was shown
during PYRICE project 2008, PYRICE II project 2012:
Using RHA to replace cement and aggregates in building applications, components of strength equal
to a reference mixture can be obtained. At the same time, a similar durability in general is achieved,
plus significant ecological benefits, due to industrial by-products use (reduction of pollution from
RHA arbitrary disposal) and decrease in the cement quantity (energy saving and CO2-emission
reduction). As the k-value for treated RHA is estimated around 1 (equal to Portland cement) or higher
(see Chapter 4 as well), it means that RHA can substitute equally cement, and by taking into account
that 1 t of cement production emits 1 t CO2, every 1 t of RHA used in building applications almost
save 1 t of CO2 emissions.
Using RHA to replace only aggregates, elements of significantly higher durability and strength can be
produced increasing slightly the production cost. However, due to increase in durability, a significant
decrease in maintenance and repair costs is expected. To this, significant ecological benefits should be
added, due to use of industrial by-products and building lifetime lengthening.
118
5.1.2 Present study
The target products, i.e., the RHA-derivatives for building applications at an order of increasing price
have as follows:
1. Production of tundish powder / insulator for steel & construction industry

2. Production of pozzolanic material for construction industry
The first choice (insulator / tundish powder production) offers a decent market price, and it requires a
minimum of RHA production modifications in order to fulfil the quality requirements for steel industry.
These are carbon content less than 5%, a high amorphous silica proportion (more than 80%), and a
particular grain size distribution upon request.
RHA is used by the steel industry in the production of high quality flat steel. Flat steel is a plate product or
a hot rolled strip product, typically used for automotive body panels and domestic 'white goods' products.
RHA is an excellent insulator and it can be also used for construction isolation applications, having low
thermal conductivity, high melting point, low bulk density and high porosity. It is this insulating property
that makes it an excellent tundish powder. These are powders that are used to insulate the tundish,
prevent rapid cooling of the steel and ensure uniform solidification in the continuous casting process.
Steel & construction market for RHA uses as tundish powder / insulator:
- The market within the steel industry is well established.
- However there are constraints to the expansion of this market due to health issues associated with
using RHA. Crystalline ash, the form preferred by the steel industry, is carcinogenic and the use of
RHA is banned in some European countries. This trend is likely to increase.
- There is more scope for development in Asian and Eastern markets, but the future size of the market
is not certain.
- Some companies are pelletising RHA, and state that this overcomes the health issues. There is
controversy over whether this is the case, but some steel manufacturers have converted to pellets.
The second choice (pozzolanic material production) offers a relatively higher market price. The fixed and
operational costs are rather low, the quality of the product can be easily ensured, and there are plenty of
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J.G. Tapali
customers in Greece and in Europe to adsorb the production. As it does not require high technology and
intensive infrastructure, it could easily be reproduced from other competitors threatening the future sales.
Cement & construction market for RHA uses as pozzolanic material:

- The cement markets are not as well developed as steel, but there is great potential for the use of RHA
in this area.
- It is currently not being used to any extent, except in the USA. Two main issues appear to be limiting
its use: lack of awareness of the potential for RHA and the quality of the product itself.
- The cement industry requires amorphous ash, so there are none of the health issues associated with
crystalline ash.
- The cement industry has to produce a consistent, high quality and standard product. This in turn
requires RHA from a controlled combustion environment, to ensure a consistent standard ash.
Producing RHA of the correct quality may cost more than producing normal ash due to boiler
modifications etc.
- In addition to the use of the ash, it may be possible to generate Certified Emission Reductions (CER-
carbon credits) when substituting for Portland cement. Portland cement requires enormous heating in
its manufacture and avoiding the energy (derived from fossil fuels) and thus carbon emitted from its
manufacture could generate an additional income stream for the producers of RHA.
RHA can also replace silica fume in high strength concrete or repair mortars: Silica fume or micro silica
is the most commonly used mineral admixture in high strength concrete. The major characteristics of
RHA are its high water demand and coarseness compared with condensed silica fume. To solve these
problems RHA needs to be ground finely into particles of 8-10 m and a superplasticizer added to reduce
water requirement.
The present Chapter deals with the elaboration of a technical and financial study and a preliminary design
for the industrial production of the RHA-derivatives for building applications, including an environmental
analysis. A conceptual design is first applied to find the best process flowsheet and estimate the optimum
design conditions: Having the appropriate methods that should be followed for the production of RHA-
derivatives, an optimum, technical and economical, design of the processes at industrial level is carried
out. The target is a technical acceptable solution at the possible lowest fixed, operational and
environmental cost. This goal is succeeded by applying a conceptual design to find the best process
flowsheet (i.e., to select the process units and the interconnections among these units) and estimate the
optimum design conditions. After definition of the operational parameters, the process flowchart is
120
constructed via a hierarchy of design decisions, namely structure of input-output, recycling, separation
and thermal integration (saving energy).
An assessment for the following techno-economical characteristics is further performed: origin, quantity
and characterization of the raw materials, proposed treatment process to produce high marketable
products, fixed cost, required personnel, operational cost, product cost, market (supply and demand,
competition), sale price, profit, financing possibilities, lifetime, etc. The limitations that may arise are
examined, such as the registration of these new materials according to EU and national regulations.
Knowing the above components, the rate of return on investment is estimated and the first conclusions for
the undertaking of this investment are drawn.
Risk assessment analyses (partial and summarized) take place and the relative elasticity analysis for
certain major cost-effecting parameters is carried out. Greater degree of detail is also provided for
elements of the current study such as: buildings, health and safety, environmental protection etc. Detailed
design of the equipment (main and supplementary) is provided as well. Thorough imprint of the
organization chart and the personnel of the unit (and thus assessment of the necessity of stuff), along with
all other cost-effecting production factors (maintenance, spare parts, consumption), reserves (raw and
supplementary), provisions and general expenses (administrative, customer support and sales) are essential
to the study. This analytical form of technical/economical study would provide:
precise demands for capital for a fixed investment
provisions for operational capitals
provisions for revenue
In the following sections, the appropriate components that compose the technoeconomical study are
presented for each one of the above targeted products, converging to final conclusions & suggestions for a
porential investment.
5.2 RHA derivatives for construction Production processes
5.2.1 Rice and RHA production
Very few cereals hold the same importance in human nutrition world wide, as rice. 60% of earth's
population has a rice-based nutrition. Rice is a primary source of food for billions of people, and ranks
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J.G. Tapali
second to cow milk in terms of production value and third after sugar cane and maize in terms of
production quantity, with the wheat ranked forth (FAO Statistical Database 2007). Globally,
approximately 600 million tonnes of rice paddy is produced each year. The annual production of paddy
rice (Oryza sativa) globally was 657,413,530 tonnes in 2007. Of this, 95% was produced by 20 countries,
as shown in Table 5.1. World rice production is expected to peak in 2008, however the increased demand
and reduction of exports will be maintaining rice highly priced in short-run al least.
Table 5.1 Rice paddy, in the 20 highest producing countries, FAO 2007.
Rank Area Production (Int $1000) Production (tonnes)

1 China 35,526,760 187,397,460
2 India 29,968,800 144,570,000
3 Indonesia 11,845,150 57,157,436
4 Bangladesh 7,981,474 43,057,000
5 Viet Nam 7,334,530 35,942,700
6 Thailand 6,357,229 32,099,401
7 Myanmar 6,224,919 31,450,000
8 Philippines 3,229,486 16,240,194
9 Brazil 2,309,714 11,060,700
10 Japan 2,310,732 10,893,000
11 United States of America 1,882,144 8,999,230
12 Pakistan 1,709,320 8,345,100
13 Egypt 1,392,410 6,876,830
14 Cambodia 1,375,592 6,727,000
15 Korea, Republic of 1,276,292 6,038,000
16 Nepal 767,014 3,680,839
17 Nigeria 652,545 3,186,000
18 Sri Lanka 645,100 3,131,000
19 Madagascar 724,660 3,000,000
20 Iran, Islamic Republic of 471,135 2,800,000
Rest of the World 7,008,994 34,761,640
Total (World) 130,994,000 657,413,530
122
Chapter 5 - PhD
D Dissertation
n
Figure 5.1
5 Chart shhowing the 9 highest rice paddy produucing countrries in 2007, FAO 2007.
Productiion of rice iss dominated by Asia, whhere rice is the

t only foood crop that can be grow
wn during thee
rainy seaason in the waterloggedd tropical areeas. Most paaddy is prodduced by Chiina (28.5%) followed byy
India (222%). Globallly, rice produ
uction is incrreasing, withh an increasee of 10% from
m 1992 20002, and 13%
%
from 20002-2007.
In Greecce, the rice paddy

p producction, importts and rice milled
m exports are given iin Table 5.2 (FAO 2007)).
A steadyy increase onn rice paddy production
p iss observed duuring the last years.
Table 5..2 Rice padddy productioon, imports and

a rice milled exports, in
i Greece, FA
AO 2007.
20005 2006 2007 2008

Production of rice paddy,
p 158,9991 179,193 1844,243 208,800
tonnes
Area haarvested, 22,2281 23,236 255,000 31,000
Ha
Rice paaddy importss, 20,163 99,404
tonnes
Rice milled
m exportss, 53,0014 67,785 699,061
tonnes
123
J.G. Tapali
Yields are affected by several factors, including the agronomy of the crop. This is influenced by the
physical and cultural environments and scale under which the rice is grown. International co-ordination
and co-operation in technological advances of rice production is providing alternatives to the limitations
of cultural practices, by the use of chemical fertilisers, insecticides, pesticides and introduction of new
varieties. Rice production is often set back by the weather, monsoons and droughts, but the effects of this
are increasingly being limited by irrigation and water control systems.
On average 20% of the rice paddy is husk (Beagle 1978), giving an annual total production of
approximately 120 million tonnes. Rice husks are one of the largest readily available but most under-
utilised biomass resources, being an ideal fuel for electricity generation and heat or steam production. The
calorific value varies with rice variety, moisture and bran content but a typical value for husks with 8-10%
moisture content and essentially zero bran is 15 MJ/kg. The treatment of rice husk as a resource for
energy production is a departure from the perception that husks present disposal problems. The concept of
generating energy from rice husk has great potential, particularly in those countries that are primarily
dependent on imported oil for their energy needs. For these countries, the use of locally available biomass,
including rice husks is of crucial importance.
5.2.2 RHA derivatives
Rice husk is unusually high in ash compared to other biomass fuels around 18-20% (Velupillai et al.
1997). Assuming a husk to paddy ratio of 20%, and an ash to husk ratio of 18%, the total global ash
production could be as high as 23,700,000 tonnes per year. The potential rice husk ash production in
Greece is thus estimated as 8,000 tonnes per year.
The ash is 92 to 95% silica (SiO2), highly porous and lightweight, with a very high external surface area.
Its absorbent and insulating properties are useful to many industrial applications, and the ash has been the
subject of many research studies. If a long term sustainable market and price for rice husk ash can be
established, then the viability of rice husk power or co-generation plants are substantially improved. A 3
MW power plant would require 31,000 tonnes of rice husk per year, if operating at a 90% capacity factor.
This would result in 5580 tonnes of ash per year. Revenue from selling the ash for beneficial use would
decrease the pay-back period for the capital needed to build the project. Many more plants in the 2 - 5
MW range can become commercially viable around the world and this biomass resource can be utilized to
a much greater extent than at present.
124
Rice husk ash has many applications due to its various properties. It is an excellent insulator, so has
applications in industrial processes such as steel foundries, and in the manufacture of insulation for houses
and refractory bricks. It is an active pozzolan and has several applications in the cement and concrete
industry. It is also highly absorbent, and is used to absorb oil on hard surfaces and potentially to filter
arsenic from water. More recently, studies have been carried out to purify it and use it in place of silica in
a range of industrial uses, including silicon chip manufacture.
RHA is a general term describing all types of ash produced from burning rice husks. In practice, the type
of ash varies considerably according to the burning technique. Two forms predominate in combustion and
gasification. The silica in the ash undergoes structural transformations depending on the temperature
regime that undergoes during combustion. At 550C 800C amorphous silica is formed and at greater
temperatures, crystalline silica is formed. These types of silica have different properties and it is important
to produce ash of the correct specification for the particular end use. There are health issues associated
with the use of crystalline ash, inhalation of which can lead to a number of diseases, the most common
being silicosis. This affects the potential markets for this type of ash.
The principles of the conceptual design have been applied for the preliminary design of RHA conversion
to insulation or pozzolanic materials; the main conclusions are given as follows:
For the production of tundish powder / insulation material low carbon content (LOI), low
crystalline content and stable quality are required. The most commonly used boilers are based
on fixed grate technologies, which tend to produce ash with high carbon content, high LOI content
and high proportions of crystalline to amorphous ash. Several adjustments on operational
parameters (temperature, feed, residence time) are required in order to meet the above
specifications. The values of these parameters, sufficient to produce RHA of the required
specifications, can be found from the pilot plant runs. Suspension fired boilers generally produce
more amorphous ash than stoker fired boilers despite the fact that they may operate at higher
temperatures. This is because the operating time at high temperatures for suspension fired boilers
is comparatively short. Commonly, in the production of highly amorphous ash, low temperatures
and fairly long burn-times are used.
In the case of RHA treatment in order to produce an upgraded material with pozzolanic properties,
only a mill is practically required. Thus, in additional to the conceptual design, a market
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J.G. Tapali
research was also performed in order to identify a suitable mill, able to meet the potential
customers requirements (mainly high fineness). Better burning conditions and/or additional
burning in order to get a whitish product are also required.
5.2.3 Flowchart for insulation materials production
Steel industry has a great potential for using RHA mostly as an insulation material or tundish powder.
Similar applications could be found in other industries and production processes, such as construction of
insulation panels, application of insulation blocks, etc. Thus, commercially, it is important to determine
and control the type and quality of rice husk ash produced in order to meet the regulations for the specific
uses. These can vary depending upon the different combustion techniques used. For example, stoker fired
boilers tend to produce higher quantities of crystalline ash, whereas similar boilers with suspension firing
produce more amorphous ash. The additional revenue stream provided by the sale of RHA may be the key
to an energy projects viability. If this is the case the appropriate technology should be chosen to produce
ash of the required type and quality for the target RHA market.
The high ash content of rice husks and the characteristics of the ash impose restrictions on the design of
the combustion systems. For example, the ash removal system must be able to remove the ash without
affecting the combustion characteristics of the furnace (especially if the ash produced is mostly bottom
ash). The temperatures must be controlled such that the ash melting temperature of approximately 1440C
is not exceeded and care must be taken that entrained ash does not erode components of the boiler tubes
and heat exchangers.
For the established market of the steel industry and the emerging market in the cement industry sufficient
data is available on the physical and chemical requirements as regards the upgraded RHA (PYRICE
project 2012). In Chapter 4, information has been provided on the characteristics of, and potential uses for
RHA.
In summary, depending on the combustion method chosen, RHA can vary from having a negative value,
where costs have to be incurred to dispose of it, to having various positive values depending on its quality
and the market for it beneficial use. The main characteristics that determine the potential value of RHA
are:
residual carbon content,
126
significant quantity of crystalline phases of silica dioxide present

mainly amorphous silica with little or no crystalline phases
Combustion of rice husks, typically in stoker fired boilers, where the ash experiences sustained
temperature above 750C leads to a significant quantity of crystalline silica in the resultant ash. The steel
market (insulation materials) is preferred for this type of ash. However, the most important characteristics
for insulation applications is carbon content (connected with LOI as explained above) and fineness. These
characteristics may vary depending on application.
In this case no specific requirements were put for an RHA of high crystalline content. This has to be
related with the fact that the crystalline content is connected with health issues (silicosis) and thus finally
is not anymore a property that is required. On the contrary, RHA with higher percentage on amorphous
phase should be produced.
According to the above specifications put by a potential customer and the RHA production characteristics
presented in previous chapters, the following preliminary design directions can be concluded:
Indistinct and vague details are often given for boiler descriptions and RHA analyses. In such cases
the value of RHA analyses in a commercial sense is minimal.
The change from amorphous to crystalline ash occurs at approximately 800C, although the process
is often incomplete until 900C is achieved.
Generally, lighter coloured ash has achieved a more complete carbon burnout.
All combustion processes devised to burn rice husks remain below 1440C, which is the RHA
melting temperature.
The chemical and physical properties of the ash may be influenced by the soil chemistry, paddy
variety and fertiliser use.
Suspension fired boilers generally produce more amorphous ash than stoker fired boilers despite the
fact that they may operate at higher temperatures. This is because the operating time at high
temperatures for suspension fired boilers is comparatively short.
Commonly, in the production of highly amorphous ash, low temperatures and fairly long burn-
times are used.
Fly ash is a fine material and is of higher marketable value since it requires less grinding than the
generally coarser bottom ash.
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J.G. Tapali
Fixed grate technologies tend to produce ash with higher carbon content, higher LOI and higher
proportions of crystalline to amorphous ash.
Basic Boiler/Furnace Operational Flowchart & Auxiliary Equipment
Rice husk transport
Combustion gas Bag

Rice
Filter
RHA silo
husk prior to
interme- packaging
diate silo Generator
Boiler / Furnace 160 kW
To combustion
chamber
Boiler Steam
A motor
Dryer
RHA airtransport pipeline
A: To parboiling process, to heat exchangers for building heating
Figure 5.2 Simplified flowsheet for RHA production as an insulation material (PYRICE 2012).
The Greek rice industry cooperating in this research has two conventional moving grate combustors in its
factories, see above general flowchart. These furnace/boiler systems have different adjustments to
operational pressure and temperatures to match parboiling production demands. The main process
performed is the incineration of rice husks produced from rice milling (20% w/w). The main purpose of
the incineration is the biomass exploitation for heat production that would cover the excessive energy
demands in both plants. The rice parboiling process is in great demand for heat (steam and drying) that
needs to be covered by the incineration process and there is also great demand for the facilities heating. To
further expand the process the company has developed an energy saving strategy in a twofold manner:
128
- the production of high added value materials from RHA, as well as,
- the production of electricity (use of steam).
The combustion is performed in a moving grate furnace that results to high crystalline silica content, large
ash particle size and high carbon content. Since there was no original plan for RHA exploitation, this type
of combustion was found to be more affordable (economically) and with higher productivity than other
types of furnaces, but also with serious disadvantages in terms of RHA quality properties. The RHA
properties have to be refined in order to meet customer specifications (for all types of RHA products).
5.2.4 Flowchart for pozzolanic materials production
Having the appropriate methods that should be followed for the conversion of RHA from a waste material
to a useful by-product with important pozzolanic properties, an optimum, technical and economical,
design of the process at industrial level was carried out. After definition of the operational parameters, the
process flowchart is constructed including input-output, recycling, separation and thermal integration. The
target is a technical acceptable solution at the possible lowest fixed and operational cost.
Production method: As the most critical unit process it could be suggested the conversion of the raw RHA
(RR) to upgraded RHA (UR) that meets the customer requirements, i.e., fineness level. Thus, this process
can be represented by the following reaction:
Raw RHA (RR) Upgraded RHA (UR) + Improper RHA (IR) (5.1)
In the above reaction, the production of an improper RHA (IR) has been also anticipated, in other words
this RHA that does not fulfil the requirements and in general its treatment is non-economically viable. The
process described by Eq. (5.1) takes place in a mill. Due to low content in free CaO no partial hydration of
raw RHA is required and thus the milling process does not include water (dry process) for hydration of
free CaO to Ca(OH)2 (for expansion prevention). Thus no water is drained into the mill, no further heating
is therefore needed at 110 oC for water vaporization, as it is necessary on other fly ashes treatment, e.g.,
high-calcium fly ashes from lignite combustion.
The temperature at which the above process takes place is that of the surrounding environment increased
by any adiabatic elevation, due to heat release during milling. Subjects of pressure and catalyst do not
129
J.G. Tapali
interfere in the present process. The process kinetics is actually defined from the residence time in the mill
in order to achieve the required fineness.
The whole production process can be divided into the following three stages:
1. Homogenization of the raw material (RR)

2. Milling of RR to final product (UR)
3. Homogenization of the final product and storage for disposal
Production rate: An initial capacity of 1000 t UR /y is considered as the basic scenario. This amount can
be obtained easily by the present production rate of RHA in factories of the Greek rice industry. Later on
a sensitivity analysis on the influence of unit capacity to cost-benefit characteristics will be performed.
Product specifications: The specifications are according to customer requirements or to the European
Standard EN-450 for use of fly ashes into concrete. These in the most of the cases are:
- homogeneity
- fineness: retained in 45m sieve < 40% bw.
- free CaO < 1 or 2.5%
- sulphates SO3 < 3%
- loss on ignition < 5%
As the production rate is estimated at about 1000 t/yr, with a solid-treatment character the batch operation
is selected instead the continuous one. It means that the specific plant for RHA treatment will operate only
for one (1) eight-hour shifts per day.
The final flowsheet, taking into account all appropriate hierarchical procedure, the specific characteristics,
and the common engineering design principles, is given in Fig. 5.3.
130
Figure 5.3 Suggested flowsheet for pozzolanic material production from RHA (PYRICE 2008, 2012).
5.2.5 Raw materials
RHA can be produced from rice husks by a number of thermal processes. Commercially, it is important to
determine and control the type and quality of rice husk ash produced. These can vary depending upon the
different combustion techniques used. For example, stoker fired boilers tend to produce higher quantities
of crystalline ash, whereas similar boilers with suspension firing produce more amorphous ash. The
additional revenue stream provided by the sale of RHA may be the key to an energy projects viability. If
this is the case the appropriate technology should be chosen to produce ash of the required type and
quality for the target RHA market. For example, the colour of the ash is important for some cement
markets where the ash influences the colour of the final cementitious product, as well as being a major
indicator of the samples residual carbon.
The high ash content of rice husks and the characteristics of the ash impose restrictions on the design of
the combustion systems. For example, the ash removal system must be able to remove the ash without
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J.G. Tapali
affecting the combustion characteristics of the furnace (especially if the ash produced is mostly bottom
ash).
Typically, the ash will contain some unburnt components as well as inert components of the husks. The
unburnt component is predominantly carbon. It is typically measured by reheating a sample of the ash in
an oven. The difference in mass of the sample before and after heating is referred to as the Loss on
Ignition (LOI). The LOI value is normally the same as the carbon content of the ash. The carbon content
of RHA varies according to the combustion process. RHA analyses from a literature search and from
analyses performed on RHA material for this study indicate carbon (or LOI) values ranging from 1% to
35%. Typically, commercial RHA combustion appears to result in RHA with 5-7% maximum carbon.
The colour of the ash generally reflects the completeness of the combustion process as well as the
structural composition of the ash. Generally, darker ashes exhibit higher carbon content (with the
exception of those that may be darker due to soil chemistry/region. Lighter ashes have achieved higher
carbon burnout, whilst those showing a pinkish tinge have higher crystalline (tridymite or cristobalite)
content.
The main factors in the various combustion and gasification processes that determine the type of ash
produced are time, temperature and turbulence. These effect all chemical changes that occur in the
combustion process including the way the ash morphology is altered.
A summary from the literature given RHA analyses is shown Table 5.3.
Chemical analyses of RHA samples from the Greek rice industry, Table 5.4, have shown a high
percentage of active (amorphous) silica, about 70% in the sample. This amorphous SiO2 is the basic
component that is of interest and all the above advanced potential applications are based on. Optimization
in RHA production has to be sought for maximum production of active SiO2 and then investigation is
required for further exploitation of the RHA.
A disadvantage of the above RHA, is the rather high loss on ignition, that is mostly owed to unburnt
carbon, and varies between 5-10%. The presence of carbon complicates some of the above applications
and some ways for its limitation under 5% must be sought. Thus, from the above initial RHA analyses,
and by studying the international literature, it seems that the present RHA, under specified production
conditions, can be converted into advanced and high-added value materials, and in any case the
132
technology risks are limited. Still remain the production and economic risks due to relevant ignorance of
pilot production and deep market characteristics (main objectives of the present proposal). Certainly, the
production of each RHA-derivative, demands new establishments and buildings as well as specialized
equipment of high operational costs, but this is also part of the current investigation.
Table 5.3 Ranges on RHA analysis from various literature sources (PYRICE 2008, 2012).
Property, analysis
pH 8-11
SiO2 (Total, %) 62-98
SiO2 (Amorphous, %) 0.2-98
SiO2 (Crystalline, %) 0.5-98
Al2O3 (%) 0.01-1
Fe2O3 (%) 0-2.8
CaO (%) 0.1-1.3
MgO (%) 0-2
P2O5 (%) 0-2.7
Na2O (%) 0-1.6
K2O (%) 0.1-2.5
TiO2 (%) 0-0.03
Cl 0.01-0.04
LOI (%) 1.5-5.5
Carbon (%) 2.7-6.4
Table 5.4 Ranges on Greek RHA analyses (PYRICE 2008, 2012).
Property, analysis
pH 7.9-10.2
SiO2 (Total, %) 73-89
SiO2 (Amorphous, %) 63-70
Activity ratio (amorphous/total SiO2) 71-93
Al2O3 (%) 0.13-0.22
Fe2O3 (%) 0.28-0.70
CaO (%) 0.67-2.25
MgO (%) 0.26-0.36
Na2O (%) 0.15-0.47
K2O (%) 0.62-1.96
LOI (%) 4-17
Carbon (%) 5-10
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J.G. Tapali
5.3 Equipment, plant site and restrictions
5.3.1 Equipment for RHA conversion to pozzolanic material
Based on the flowchart, Fig. 5.3, it is possible to identify the main and auxiliary equipment required. In
this way, the type is determined as well as the size of equipment is estimated, i.e., type and size of mill,
cyclones and silos, transport equipment and compressors. At the same time indications are provided for
construction materials of this equipment in order to meet their working conditions. The requirements for
the auxiliary equipment are recorded (storage, transport, possible controls, etc.) as well as the necessary
quantities of energy (electricity, fuel and compressed air) and water. Of course at this stage it should be
considered if all or part of the required main and auxiliary equipment exists and is probably available.
Following, the basic units of equipment will be examined: the homogeneity system and the mill, based on
literature data.
a. Collection & RHA homogenization
The most serious problem that needs to be addressed in order to use RHA, is the great fluctuation in
RHAs composition. This property characterizes more or less, nearly all ashes that are produced from
biomass, coal or lignite. To tackle this problem, production must contribute to the effort of homogenizing
rice husk that will be burned. This effort is essential anyway, for better energy exploitation of fuel. In this
context, the following are proposed:
Strict quality control of raw and treated RHA. For this purpose, close cooperation between
production and RHA exploitation unit is required to ensure, as much as possible, consistent quality
of rice husk and consequently consistent quality of RHA.
High degree of homogenization of the raw ash before its supply to the grinder. In order to address
the problems of homogeneity while operating the grinder for the processing of ash, a system of
continuous monitoring of raw ash should be organized. Continuous sampling should take place
through a special device that can be adjusted to the supply lines of the silos. These samples should
be checked for their sulphates (SO3) and the very high levels of free CaO, while forming an opinion
about the exact quality of the ash that the next few hours will go through grinding. Samples that do
not meet up, for various reasons, the highest levels of standard values (e.g., 3% for sulphate or 2.5%
for free CaO) should be discarded.
134
High degree of homogenization of treated ash for sale. The ash can been stored in different silos in
layers, so that the final product that will result from each silo will be as homogeneous as possible.
Similarly, for this project and in order to ensure product homogeneity, a series of six (6) silos for storing
raw material and a series of three (3) silos for storing the final product are proposed. The raw
material for processing will result from all six silos containing raw material and the final product for
distribution will result from all the three silos containing the final product.
b. The grinding mill
The RHA grinding mill is considered to be a critical process. The study for the grinding plant of Greek
Public Electricity Corporation (DEI) at Ptolemais as well as the organization and the equipment of the
chemical laboratory for quality control of the ash were all part of the contact work for the construction of
the dam by the consortium AEGEK - HIDROGRANJA - ASI RCC under the supervision of DEI. The
unit consists of a closed-circuit grinding mill with additional supplementary equipment. The mill has three
apartments and the nominal capacity is 16.7-23.0 t / h for the projected product fineness. Note that the
mill was tested on productions 30t / h at which it responded with the subsequent modification of fineness
provided that a large reduction of free CaO is not required. Its dimensions are (diameter x length)
2.6x12m and operates with a degree of filling 30% which is covered by grinding bodies with dimensions
30 and 40 mm (total weight 42 t) and the material that has a bulk density of 860 kg/m3. The movement of
the mill is achieved by an engine with power 720 kW.
For the present study, a similar grinding mill is suggested to be examined of proportional capacity.
Having however performed an extended literature survey and experimental investigation vibration-type of
milling systems is suggested. In the Fig. 5.4 images of vibratory grinding mills are given.
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J.G. Tapali
Figure 5.4 Vibratory grinding mills for RHA efficient milling to sub-micron level; commercially
available by Bulton (left) AMKCO (right).
5.3.2 Plant site
The choice of the plant site has a definite influence on the project success. The main criteria for the
selection of the plant site are to minimize the cost of production, transport and storage. If the under design
unit has been decided to be an expansion of an existing industrial site, then the design needs to be
compatible with any existing facilities. As such are considered to be supplies of fuel, steam, cooling water
and other sub-cooling means, the electricity supply as well as the waste treatment facility. If the unit is to
be constructed in a new independent site then the choice of the location should be made after considering
a number of factors:
Land cost. The cost for purchasing land or renting premises in some cases contributes significantly to the
definition of the overall fixed costs.
Purchase of raw materials. Placing the plant near the source of raw materials means reduction in the costs
of transport and storage. The same is true in the case of auxiliary materials, fuel, packaging materials, etc.,
depending on the type and characteristics of the business.
136
Product purchase. It is preferable to install the plant near the main markets mainly because it reduces the
distribution cost. It is common to have plants that produce intermediate products elsewhere for specific
reasons and plants that produce the final products to be close to major urban centers.
Infrastructures of area. The candidate area should gather a number of characteristics for accommodating
the plant. These are mainly: an industrial zone, capable workforce of different education and experience,
accommodation for staff, training opportunities, leisure and health care facilities, energy and water
supplies, waste treatment facilities, appropriate suppliers of materials and services, and good
transportation network. The existence of a port or highway connections are also key elements.
Characteristics of environment. The climate has relatively little effect on the choice, but the cost of
heating, cooling or insulation to maintain stable conditions in the production and storage area, the cost of
corrosion protection in coastal areas or wetlands and any transportation exclusion of the factory by bad
weather should be considered. Another issue that should also be considered is whether the land is suitable
for the construction of industrial buildings and take into account the seismic characteristics of the area.
Investment incentives and tax exemptions. Clearly the establishment of the plant must be within the areas
that are foreseen by the law depending on the type of industry. Greece is divided into categories of
industrial areas, which vary depending on the location and incentives that encourage or discourage are
provided. The incentives that are usually provided in order to invest in areas where industrial development
is sought (mainly remote and economically problematic regions) are grants, interest subsidies, tax
exemptions and increased depreciation, which are often quite powerful in selecting the final location of
the unit.
Based on the above analysis and because the raw material is obtained exclusively from the Greek rice
industry, it is expected that the site plant for RHA treatment and the production of added value materials
will be at close distance from the factories. The proximity allows direct supply of raw ash through
pneumatic system. Furthermore, the communication between technical staff of both companies is an
important issue for the development of the production (benefits: reduction of transport, quality control and
production level, management benefits, etc.). Also, the criteria which include development incentives and
tax exemptions are considered as very important for the selection of an alternative location for this
investment. There are areas with good access to key raw materials and product markets, where important
support is provided for the assets (and operating) costs of around 45%. For example, the industrial areas
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J.G. Tapali
of Astakos and Sindos concentrate enough of these positive attributes so as to qualify as an alternative
location for the site plant.
5.3.3 Restrictions
a. Patents and legal restrictions
This issue is not a direct part of technoeconomical analysis, but it is possible to exclude certain processes
or products. If relevant patents exist then these must be identified and loyalties must be paid. No similar
techniques were patented for pozzolanic material production from RHA; leaving thus space for potential
patenting from the present work.
The resulting product (RHA for structural applications) is according to the European Standards EN 450.
Through EN-450, the technical specifications of the material are provided, as well as the frequency and
the process control, compliance criteria and other features that ensure the desired quality. This means that
through EN-450, the legal constraints arising from the use of the product are covered. It should be noted
that Greek standards are expected, which are considered less stricted" than EN-450. Thus, RHA complies
with these standards since it already complies with European EN-450.
Additionally, the producer may adopt a quality system such as ISO 9000, which increases overall the
reliability of the manufactured products.
b. Operating limitations, security and environmental protection
In many cases the design should be done with certain constraints that are either associated with the proper
operation of the facility or with safety issues and environmental protection. With regard to operating
limitations, for example, the operating conditions under which some materials can polymerized and create
deposition heat exchange surfaces, or to other units of the process need to be known. Other materials can
form carbon deposits and deactivate the catalyst. Also, materials with high toxicity and high corrosivity
can affect the design proposal. Therefore the engineer designer must take into account these operating
limitations and plan within acceptable limits.
Also the security issues which introduce similar restrictions are very important. It should be noted that an
engineer not only plans properly and economically, but above all in a safe way. The safety is connected
138
with the avoidance of accidents that cause injuries to personnel or the environment. Clearly, conditions of
operation within the limits of a mixtures ignition should be avoided. Similarly, the designer must avoid
negative impact on the environment, and various emissions of the process (gaseous emissions, liquid and
solid wastes, noise and thermal pollution) must be within the predefined limits. Specifically:
c. Health & safety at work
When engineers design a unit, a main issue is the creation of a perfectly healthy work environment that
minimizes the risk of accidents during work. During the production of RHA, the silica in the ash
undergoes structural transformations depending on the conditions (time, temperature etc.) of combustion.
At 550C 800C amorphous ash is formed and at temperatures greater than this, crystalline ash is
formed. These types of silica have different properties and it is important to produce ash of the correct
specification for the particular end-use. There are health issues associated with the use of crystalline ash,
inhalation of which can lead to a number of diseases, the most common being silicosis. Amorphous ash
does not contain the more harmful forms of silica, but can be a respiratory hazard, particularly if finely
ground. In this case, almost 100% of RHA produced is in amorphous state and not in crystalline.
Exposure Limits
The UK Health and Safety Executive (HSE) has assigned a maximum exposure limit of 0.3mg/m3 for
crystalline silica, expressed as an eight hour time weighted average [1]. The USA Permissible Exposure
Limit (PEL) is 10mg/m3 divided by the % SiO2 + 2. The UK HSE does not have regulations relating
specifically to RHA, and state that the rules for silica should be followed. The UK HSE advises that
samples should be taken if dust levels are expected, and that they should be regarded as significant if they
are above 0.1mg/m3. In this case dust control levels should be implemented.
Occupational Safety & Safety Administration (OSHA) has an established PEL, which is the maximum
amount of amorphous silica to which a worker can be exposed as the percentage of amorphous silica in
the dust rises. The term SiO2 refers to the percentage of amorphous silica in the sample. When the
amorphous silica content is at or below 5.33% the total dust (Particulates Not Otherwise Regulated) PEL
of 15 mg/m3 should be used.
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J.G. Tapali
The project PYRICE II (2012) aimed to the complete RHA management by capturing and converting the
produced RHA to useful products. In addition to this complete solution a Specific Programme for
Capturing and Controlling Dust at source was recommended to control dust exposure, including:
Dust control programme which includes measures that ensure that workers are not exposed to dust.
There a number of simple control measures that can be taken. More specifically reducing employee
exposure to dust can be accomplished by three major steps: prevention, control systems, dilution or
isolation.
Training and information to workers
Equipment maintenance programme.
Personal protection & first aid.
Personal hygiene facilities, eating & clothing
Record keeping.
Regulated areas/warning signs.
d. Environmental protection
When designing a unit in Chemical Industry, the main principle that is followed is that the environment
should not be affected (in a negative way) in any way. For this reason it is required by the law to create an
Environmental Impact Assessment (EIA). Thus the designer engineer should identify all possible sources
of pollution that the unit can create and exclude them. Such pollution can be:
Chemical (emission of hazardous or odour gases, liquid waste containing substances that alter the
physiology of the recipient, creation of solid waste which are difficult for disposal)
Thermal (disposal of high temperature water to the environment)
Sound (noise emission)
Aesthetic (no architectural adaption of the unit to the environment).
Gas emissions, dust and noise are issues that the engineer must deal with when designing a unit
(absorption towers, filters, insulation, etc.). All waste will either be processed within the factory or will be
directed to a common treatment plant that is shared with other factories (e.g. in an industrial area).
Regarding the permitted levels of gaseous and liquid waste, general and local regulations exist, the quote
of which is beyond the limits of this study.
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5.4 Organizational structure, fixed and operational cost
5.4.1 Organizational structure and personnel
From the analysis in section 5.2, it is clear that the process should be designed as batch operation,
primarily because of capacity (production rate). So the proposed operation for the case of RHA conversion
to insulation and/or pozzolanic material is one shift daily (8h), 5 days per week, 47 weeks per year (5
weeks closing of factory for maintenance). Total production days: 235 per year. This particular production
could be either a separate branch on Greek rice industrys activities or a separate subsidiary company of
the Greek rice industry with objective to carry out these particular businesses.
In the latter case, a separate Direction Scheme is required. It is suggested a commercial company of Ltd or
SA. The companys direction will be performed by a 5-member Board of Directors (President and four
members), in cooperation with the General Manager of the plant.
The following organizational scheme is suggested:
1. Plant Management
Board of Directors
General Manager
2. Administrative & Financial Services

Secretariat
Supplies - Personnel
Accounting
3. Production Department
Unit of RHA treatment and homogenization
Unit of packing and loading - Storages
Maintenance unit
4. Quality Control
Sampling
Analyses
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5. Sales Department
Sales
Marketing / After sales support
The distribution of personnel in the above departments/ services is as follows:
1. Plant Management (1+5)

1 General Manager
(plus 5 members of Board of Directors)
2. Administrative & Financial Services (2)

1 Administrative employee (Secretariat - Supplies - Personnel)
1 Accountant
3. Production Department (4)

1 Operator for panel & loading (Unit of RHA treatment and homogenization)
1 Worker (Unit of packing and loading - Storages)
1 Driver ( Products transportation)
1 Technician (Maintenance unit)
4. Quality control (1)

1 laboratory chemist
5. Sales Department (1)

1 Employee for sales & marketing
Apart the BoD, total 9 persons are required of which:

1 General Manager
4 Executives-Administrative Officers - Scientists
2 Operators-Technicians
2 Workers-Drivers
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5.4.2 Calculation of fixed costs and initial working capital
The purpose of this section is to provide the investors an understanding of the expenses that will occur and
to estimate the financial viability of the project. The idea is to use this unit both for insulation materials
production (having already a rice husk burner) as well as for the production of pozzolanic materials; it is
thus an advanced unit that involves a milling line. An average capacity of the unit is considered to be:
1000 t/y. We also consider as a batch process: one shift (8h) per day, 5 days a week, 47 weeks a year (5
weeks the factory shuts down for maintenance). Total production days: 235 per year.
The creation of an industrial plant requires expenditures for studies elaboration, purchase of land and its
configuration, purchase and installation of equipment, interfaces, components, etc. The total cost that is
required from the stage of capturing the idea until the realization of a production unit, just before the start
of its normal operation, is actually the establishment capital. This is divided into the fixed capital and the
initial working capital. The fixed capital refers to costs for the acquisition or construction of equipment
and their installation. The initial working capital refers to costs that are required in order for the
production to achieve a level of normal operation. Usually, from this point and then only operating costs
and revenues from the sale of products exist.
The fixed capital, C (or fixed costs) is divided into components, which are summarized below (cost of
studies and establishment are included). All values are referred to real values after market research and
gathering quotation from various suppliers. The currency used in all values is the euro ().
Installations and machinery

Electromechanical equipment - mill depreciation in 10 years 75,000
Installations piping, 13% of basic equipment (10 years) 10,000
Equipment for quality control laboratory (10 years) 28,000
15 homogenization silos - storage, 50 t each (10 years) 82,500
Packing-loading unit (10 years) 28,000
1 loading machine, clark (10 years) 10,000
Subtotal 233,500
Buildings & land

Offices, laboratory, storage & buildings for equipment 47,000
Fencing -
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Land property (own property) -

Subtotal (depreciation in 25 years for everything- out of land property) 47,000
Total 280,500
10% unpredictably 28,050
Total fixed cost, C 308,550
The initial working capital refers to the following expenses:
- Test operation: The cost for using staff at the stage of test operation.
- Raw materials: The cost of raw and auxiliary materials required from the start of production until
the generation of revenue from their sale.
- Labor and administrative costs: Includes wages and salaries for the period mentioned above.
- Disposal of products: The storage, advertising (and sometimes transport) costs required for the
products to reach the buyers.
The initial working capital as mentioned, is required to cover operating expenses for the period between
the start of production until the generation of revenue from product sales (we assume a six month period).
It covers the cost of raw and auxiliary materials, wages and salaries, the cost of the product delivery as
well as the test operation cost. In order to estimate the initial working capital the individual components
outlined above need to be assessed. However, this is not possible at least not until the design has
proceeded satisfactorily. To overcome this problem, the initial working capital, IC, is calculated
approximately as a percentage of fixed capital, C:
IC = (0.05-0.30) C (5.2)
Usually a factor equal to 0.18 is taken into account. Estimations are in euro ():
Initial working capital, C 55,540
Thus, the establishment capital is estimated as follows:

= total fixed cost + initial working capital
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= 308,550 + 55,540
= 364,000
In the case that an establishment or fixed cost is sought for another smaller or higher production rate
(capacity) then the simple method of proportionality could be used. This method reliable for first
approximations is based in the following equation:
n
C 2 C1 Q2 /Q1 (5.3)
where, Q1, Q2 : capacities (t/y), C1 : fixed (or establishment) capital for capacity Q1, C2: fixed (or
establishment) capital for capacity Q2, and n a statistical parameter. The exponent n varies depending on
the kind of the investment, according to historical data. For chemical industry parameter n equals usually
to 2/3; that is the reason for calling this method as method of 2/3.
5.4.3 Calculation of the operational cost
Revenues from sales, R (/y, i.e. per year) may be assessed upon market research, which will determine
both the price and quality of products that the customer wants. For the purpose of basic calculations, the
price can be determined from literature and from similar undertakings abroad or from direct information
from the potential customers and market (see section 5.5). For the present case the revenues are:
Revenues, R (420 /t * 1000 t/y) 420,000
The operational cost, OC (/y) includes a number of elements which are provided in Table 5.5. The same
table estimates approximately operating cost elements with the use of factors. It should be noted that in
literature, numerous factors for all cost elements with significant differences exist, thus creating
considerable uncertainty in calculations. For this reason, their widespread use is avoided. The factors in
Table 5.5 are average values from literature which have been modified according to cases which have
been applied in Greece. In order to calculate the operational cost it is essential to first determine (at least)
the mass and energy balances.
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Table 5.5 Operational cost elements.
Description Calculation methodology

1. Raw & auxiliary materials Calculation from mass balances
2. Energy Calculation from energy balances
3. Manpower Calculation
4. Labor costs 0.05C*
5. Administrative expenses 0.50 of element 3
6. Insurance 0.01C*
7. Depreciations 0.10C*
8. Interests Calculation
9. General expenses 0.03R**
10. Taxes Calculation
* C : fixed cost, **R : revenues
Regarding the elements of the operational cost, one can observe the following. All values are referred to
real values after market research and gathering quotation from suppliers. All values are in /y.
Raw and auxiliary materials: Refers to all necessary materials (raw - auxiliary materials, intermediate
products) from the processing of which products will result. The calculation of this element is easy with
the use of balances and cost of materials. RHA has a potential for selling at a lowest price of 70/t, thus it
has to be charged to the operational costs as price for raw material
Untreated RHA, R (70 /t * 1000 t/y) 70,000
Energy: Includes solely the power which together with raw - auxiliary materials are the variable expenses
of the operational cost, while the remaining elements in Table 5.5, are the semi-elastic or constant
(inelastic) expenses. The variable expenses vary depending on the operational capacity of the plant
(production rate), while the constant expenses are independent from it. We assume industrial use of
medium voltage power (B1B and B2B) from the Public Power Corporation (DEI).
Mill power (234 kWh/t * 0.1/kWh * 1000 t/y) 23,400
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Power balance (33 kWh/t * 0.1/kWh * 1000 t/y) 3,300

Total 26,700
Labor costs: Refers to the staff which works exclusively in the production. The calculation of the
manpower is relatively easy and requires little experience. The number and the salaries of workers depend
on the particular characteristics of the country (e.g., institutional framework, productivity). These are
calculated based on average values which also contain insurance. They are calculated directly as there is
the relevant info, see section 5.4.1.
4 technicians - workers * 1,400 (average) /month * 14 months: 78,400
Maintenance: Includes all expenses for regular maintenance, and repairing of damages. The cost of
maintenance is assumed to be equal to 5% of fixed capital.
Maintenance (0.05 * 233,500): 11,670
Administrative expenses: This element includes the expenses incurred for the support of production
(administrative staff, offices, sales network, etc.) and is typically considered to be equal to 50-60% of the
labor cost, however in this case it is calculated directly as there is the relevant info, see section 5.4.1.
1 director * 2,000 /month * 14 months 28,000

1 chemist- R&D consultant * 1,400 /month * 14 months 19,600
3 administrative staff * 1,400 (average) /month * 14 months 58,800
Compensation for President and BoD members *- /m x14 months -
Total: 106,400
Insurance fees: Refer to the plant site and the products. Is it possible to assess its value from market
information, but also it may accurately be calculated as 1% of fixed capital.
Insurance (0.01 * 233,500): 2,330
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Depreciation: Expresses in an accounting manner, the return of the fixed capital. There are different
methods of calculation, among which the simplest is the linear depreciation. The depreciation periods
vary for the different assets, and are regulated in a legislative way. With the (realistic) assumption that the
lifetime of a chemical industry is 10 years and with the use of the straight-line method, a 10% annual
depreciation of the fixed capital is calculated. Here, we have defined the depreciation years during the
calculation of fixed capital. We consider linear depreciation with zero residual value.
Depreciation (0.10 * 233,500+0.04 * 47,000): 25,230
Interests: Refers to the interest of the initial working capital and to the interest of loans for the purchase of
equipment. The calculation is easy if the initial working capital and the rate of interest for various types of
loans is known. At this point the interest is not calculated.
General costs: These are the costs for research and development (R&D), sales promotion and royalty
payments for use of technology or product label. General costs vary considerably depending on the
product and the business policy. Approximately, the general costs may be considered to represent 3% of
revenues.
General costs (0.03 * 420 /t * 1000 t/y): 12,600
Taxes: The tax rate is regulated legislatively in each country. In Greece, the tax rate is approximately 30-
40% (although there are slight differences depending on the type of business). The tax is calculated on the
amount obtained when deducting the operational costs excluding taxes from the income. Taxes (T) can be
calculated as follows:
= 0.30 (R OC) (5.4)
where, R : revenues, OC: operational cost (excluding taxes), i.e., the sum of 1-9 components of the Table
5.5.
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According to above estimations, the total operational cost, excluding taxes can be calculated as follows:
Table 5.6 Operational cost details for production of pozzolanic materials
Cost description /y
1. Raw and auxiliary materials 70,000
2. Energy 26,700
3. Labor costs 78,400
4. Maintenance 11,670
5. Administrative expenses 106,400
6. Insurance fees 2,330
7. Depreciation 25,230
8. Interests -
9. General costs 12,600
Operational cost (no taxes), OC 333,340
5.5 Market, competition and sales
The steel and cement industries are identified as having the most potential for an adequate value, large
market; issues discussed earlier in section 5.2.
Prices for RHA being sold to the steel industry are commercially sensitive and thus hard to determine.
N.P.Singhania in India is selling RHA at US$150/t, delivery at Calcutta port, India. Other estimates of
RHA on the world market are approximately $200 per tonne of ash, although it has been said that Thai
RHA is worth US$300-400/t.
The cement markets are not as well developed as steel, but there is great potential for the use of RHA in
this area. It is currently not being used to any extent, except in the USA. Two main issues appear to be
limiting its use: lack of awareness of the potential for RHA and the quality of the product itself. The
cement industry requires amorphous ash, so there are none of the health issues associated with crystalline
ash. The cement industry has to produce a consistent, high quality and standard product. This in turn
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requires RHA from a controlled combustion environment, to ensure a consistent standard ash. Producing
RHA of the correct quality may cost more than producing normal ash due to boiler modifications etc. In
addition to the use of the ash, it may be possible to generate Certified Emission Reductions (carbon
credits) when substituting for Portland cement. Portland cement requires enormous heating in its
manufacture and avoiding the energy (derived from fossil fuels) and thus carbon emitted from its
manufacture could generate an additional income stream for the producers of RHA.
In the already opened market for building applications, RHA can substitute for silica fume, exhibiting
similar properties, in various applications as highly pozzolanic material: specific types of concrete,
shotcrete, self-compacted concrete, high-strength, high-performance concrete, repair mortars, etc. The
market price of silica fume of 500 /t is very attractive. The production of lightweight construction
materials and insulation from RHA has potential, but current use is not widespread and there is limited
knowledge of the methods used. Further research may develop this commercially, but not in the short
term.
The cement industry has to produce a consistent, high quality and standard product. This in turn requires
RHA from a controlled combustion environment, to ensure a consistent standard ash. Ash of a consistent
quality is not readily available and is therefore not used by the cement industry. There are many other
cheaper and more abundant pozzolans available. A waste product from coal fired power stations is
pulverised fly ash (PFA). It is abundant and cheap and is therefore often used as an admixture in high
strength concrete. Ground granulated blast furnace slag produced from iron smelters is also highly
pozzolanic and available. However, for high strength and quality, silica fume is preferred, for which
RHA is a potential substitute and therefore a focused market research on silica fume is required.
The Europe and world producers are presented in the previous chapter; however the World Leader
Producer of silica fume is Elkem Materials in Norway (see http://www.materials.elkem.com/ ). Elkem
Materials is the globally dominating microsilica supplier and a leader in the marketing and
implementation of Elkem Microsilica and its application technology worldwide. Elkem Microsilica is one
of the principle products supplied by Elkem Materials. It finds a wide range of applications in high-
strength concrete, other building materials such as roof tiles and facade cladding, and fire-proof products
for heavy industry. Microsilica is also used for sealing tunnels and drilling oil-wells. This product
comprises microscopic particles collected by filters downstream from the smelting process in silicon and
ferrosilicon plants. Adding it to concrete and other materials increases their density and wear resistance,
which extends the life of structures. Microsilica has been delivered by Elkem to a number of major
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projects in Norway and internationally, including the resund/Great Belt connection. Elkem Materials
also produces Ceramite, a fire-proof material which is particularly heat-resistant and hard-wearing.
Treatment technology has been supplied by Elkem to industries world-wide for many years, and the
company is currently involved with major filtration projects in China. Elkem Materials has a global
distribution network, represented by our sales offices, distributors and agents.
No silica fume is produced in Greece; there is only importation of the material from the distribution
network of Elkem Materials. The market price for silica fume in Greece is 500 /t.
Market opportunities for RHA as a pozzolanic material:
1. Addition to cement
a. adding RHA as pozzolanic material: up to 30%
b. incorporating RHA in the low energy cement production, like belitics and other types.
2. Addition to concrete & mortars

Production of several concrete types as a direct reactive addition as a fourth component in the mixture of
raw materials of ready mixed concrete. Its potential use is particularly important and economically
attractive in:
High strength concrete (HSC)
Shotcrete (Gunite)
Self-compacted concrete (SCC)
Repair mortars
Success key:
There is already a very good material on the market with exceptional properties: silica fume (Elkem
Materials, 500 /t). The aim is to make RHA similar to (or replace) silica fume (SF or microsilica).
RHA costs about - 40 /t for handling and safe disposal. For the case of insulation and pozzolanic
materials production the following product prices are foreseen:
- According to real market and sales from the pilot production of tundish powder or insulators
for steel industry from the Greek rice industrys market prices of 70-140 /t can be achieved
(Solution A: Development of upgraded and standardized RHA as insulator /tundish powder for
steel industries, insulation panel constructors, etc.).
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- According to real market and contacts with potential customers (successful test from ISOMAT
SA: behavior 5-20% better than commercial silica fume) the price range for pozzolanic materials
derived from RHA is 300-420 /t, depending on quality (fineness, color) (Solution B:
Development of upgraded and standardized RHA as pozzolanic material for mortar and concrete
industries, constructors, etc.). As the market price for silica fume in Greece is 500 /tonne a
feasible, good price to use as a scenario basis in the present technoeconomical analysis is 420
/t for RHA as pozzolanic material for building applications.
5.6 Cost-benefit analysis and evaluation
5.6.1 Expected profit
An approximate estimation of the expected profit (per unit or per year) is calculated, as well as the return
on investment is evaluated, based on all the above data, as this is basic criterion for the actual
implementation of the investment. Based on the analysis performed in sections 5.4 and 5.5, the following
results are drawn regarding production of 1000 tonnes per year of pozzolanic material (almost 100%
conversion of RHA to pozzolan):
Table 5.7 Economical outcome of the investment for pozzolanic material production.
Economical parameter Results for a capacity 1000 t/y

Total fixed cost, C () 308,550
Initial working capital, C () 55,540
Operational cost (no tax), OC (/y) 333,340
Revenues, R (/y) 420/t * 1000 t/y= 420,000
Taxes, [ = 0.3(R OC)] (/y) 26,000
Net profit, ( = R-OC-T) (/y) 60,660
Return on investment, ir (%) 16.7
Payout period, (years) 6.0
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5.6.2 Evaluation of the investment
Sometimes it is necessary to choose among different alternatives for an investment project, or even to
rank various investment programs in order to determine the priority for their implementation. Depending
on the investor, the selection and assessment criteria differ. When the investor comes from the public
sector in addition to economic criteria, social criteria are also examined, whereas when the investors are
from the private sector economic criteria are examined.
The investment decision is a critical process due to the fact that the values of certain factors need to be
assessed, such as:
Plant capacity. The capacity depends greatly on the demand of the product. So if the capacity is greater
than the demand, the fixed cost increases and the need to operate at lower capacity becomes obvious.
Similar problems occur when the capacity is less than the demand of product.
Implementation time. The timing of the investment is crucial and there are cases that it affects its viability.
For instance, if there is increased demand for a product, then the proper conditions for implementing the
relevant project are set. However, if investment fails to be implemented on time then it is possible that the
corresponding demand will be satisfied through the availability of another product or the consumer
preferences might change. Finally, problems may arise in the opposite case (immediate implementation of
investment) as well, as the product demand may be a temporary phenomenon.
Despite the uncertainty that accompanies an investment decision, it is possible to measure the economic
efficiency based on the assumptions that have been made (capacity, products price, etc.). The criteria or
methods that are presented below give the opportunity to an investor or sponsor to determine the
efficiency of the under evaluation project and compare it with other standards or alternative investments.
From the existing methods of economic evaluation of investments, the most common will be used: the
method of return on investment rate and pay back period.
a. Return on investment
The return on investment is defined as follows:
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ir = K / (C + IC) (5.5)
where, K: the annual net profit (revenues - total operational costs), C: total fixed cost of investment, and
IC: the initial working capital. Obviously among two or more alternative investment plans, the one with
the greater ir will be selected. When considering a single investment plan then ir should be greater than a
minimum acceptable rate of return which is set by the company. This method ignores the value change of
money as a function of time.
Based on the estimated data, the ir for this investment is calculated and presented in Table 5.7.
b. Payout period
With this method, the time needed to recover the establishment capital is determined from the generated
revenues during the operation of the facility. Quite simply, the payout period, , is evaluated as follows:
= (C +IC) / K (5.6)
Among two or more alternative investment plans, the one with the shorter will be selected. Based on the
estimated data, the for this investment is calculated and presented in Table 5.7.
c. Evaluation of investment
From the above results the following conclusions are observed:

- The rate of return on investment is much higher than the current bank interest, fact which ensures that
the investment is viable and it is suggested to be undertaken (if a sensitivity analysis is also positive).
- The payout period is considered as satisfactory, given that the main part of the equipment is new, and
for its estimation depreciation has not been included in profit.
5.6.3 Sensitivity and risk analyses
Having a first positive result suggesting to undertake the investment, the positive limits should be
identified and evaluated, as well as the influence of operational or market parameters on the investment
outcome.
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a. Effect of capacity
The effect of capacity (production rate, t/y) is the first analysis that should be performed as it gives
essential information and estimation of break-even point, height of the potential losses, height of the
maximum profits and efficiencies, and the targeted point of operation.
In Table 5.8 the investment characteristics are presented as a function of capacity. For a capacity of 500
t/y no profit but losses are estimated. For 2000 t/y a return on investment of 36% is estimated, whereas
for 4000 t/y (maximum total production in both Greek rice industrys factories) a very high return on
investment 57% is estimated offering profits of 470,000 with a payout period of less than two years.
In Fig. 5.5 the rate of return on investment is given as a function of capacity, showing the specific curve
type. One significant outcome from this figure is the estimation of the break-even point, as Q=532 t/y,
that capacity where zero profits are estimated (i.e., revenues=expenses). However, no operation is
recommended for a capacity less than 700 t/y as it gives return on investment lower or equal to a bank
interest.
Table 5.8 Dependence on capacity of the investment characteristics for the pozzolanic material
production (product price 420 /t).
Economical parameter Q= 500 t/y Q= 1000 t/y Q= 2000 t/y Q= 4000 t/y
Total fixed cost, C () 213,130 308,550 460,370 707,920
Initial working capital, C () 38,364 55,540 82,870 126,350
Operational cost (no tax), OC(/y) 215,810 333,340 562,722 1,012,460
Revenues, R (/y) 210,000 420,000 840,000 1,680,000
Taxes, [ = 0.3(R OC)] (/y) 0 26,000 83,180 200,260
Net profit, ( = R-OC-T) (/y) -5,810 60,660 194,090 467,280
Return on investment, ir (%) - 16.7 35.7 56.5
Payout period, (years) - 6.0 2.8 1.8
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70
60
50
Return on investment, IR (%)
40
30
20
10
0
0 500 1000 1500 2000 2500 3000 3500 4000 4500
-10
Production rate, Q (tons of pozzolanic material / year)
Figure 5.5 Return on investment vs. production rate for pozzolanic material production from RHA.
b. Effect of product price
In Table 5.9 the investment characteristics are presented as a function of product price (for a stable
production of 1000 t/y). The break-even point for this case is for P=330 /t, a product price where zero
profits are estimated (i.e., revenues=expenses). However, no operation is recommended for a product
price less than 360 /t as it gives return on investment lower or equal to a bank interest.
For a product price of 500 /t (maximum price equal to silica fume value) a high return on investment
32% is estimated giving a payout period of about three years.
c. Effect of operational parameters
At this point the comparative contribution of each operational component to total operational cost is
illustrated. In Fig. 5.6, such a diagram is given. It is observed a rather rational and no-risk hiding
disribution. Among the four more importants parameters administrative expenses, workpower, raw
materials, and energy can be distinguised. None of these could cause a potential risk to the investment, as
raw material is a property of the Greek rice industry and all others cannot threat this specific investement.
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Table 5.9 Dependence on product price of the investment characteristics for the pozzolanic material
production (Q= 1000 t/y).
Economical parameter P=330 /t P=360 /t P=420 /t P=500 /t

Total fixed cost, C () 308,550 308,550 308,550 308,550
Initial working capital, C () 55,540 55,540 55,540 55,540
Operational cost (no tax), OC(/y) 330,640 331,540 333,340 335,740
Revenues, R (/y) 330,000 360,000 420,000 500,000
Taxes, [ = 0.3(R OC)] (/y) 0 8,540 26,000 49,280
Net profit, ( = R-OC-T) (/y) 0 19,920 60,660 114,980
Return on investment, ir (%) 0 5.5 16.7 31.6
Payout period, (years) - 18.3 6.0 3.2
9.Generalexpenses 10.Taxes
4% 7%
1.Rawmaterials
8.Interests 19%
0%
7.Depreciation
7%
6.Insurance
1%
2.Energy
7%
5.Administrativecosts
30%
3.Laborcosts
22%
4.Maintenance
3%
Figure 5.6 Comparative distribution of various operational components for pozzolanic material
production from RHA (Q=1000 t/y, P=420 /t).
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5.6.4 Cost-benefit analysis for RHA valorisation as insulation material
Depending on the combustion method chosen, RHA can vary from having a negative value, where costs
have to be incurred to dispose of it, to having various positive values depending on its quality and the
market for its beneficial use.
The main characteristics that determine the potential value of RHA as an insulation material are:
- residual carbon content,

- significant quantity of crystalline phases of silica dioxide present
- mainly amorphous silica with little or no crystalline phases
Given the premise that a viable rice husk fuelled power plant is to be built (or to be re-arranged in order to
meet the above requirements), the cost-benefit resulting from increased expenditure to produce an RHA
with higher value than would otherwise result is assessed in this section.
In order to examine the cost benefit analysis for RHA, we have chosen a generic rice husk fuelled power
plant sized to produce 3MWe (net) has been chosen. Unless stated otherwise, the analyses use the
following assumptions:
- ash content of fuel is 18%

- annual operating time of plant 7,500 hours
- all prices are in
In order to put into perspective the additional revenues attributable to RHA use, it is useful to keep in
mind that, if electricity has a value of 0.05 /kWh and all the plant output is sold at this price, the annual
revenue from electrical sales is 1,125,000 .
a. RHA disposal Negative benefit
The predominant reason why RHA would only be suitable for disposal is when its residual carbon content
exceeds 7%. Based on the power generation technologies examined within the scope of this work, those
that seem to result most often in a higher residual carbon content are gasifiers.
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A plant producing 3MWe using gasifier technology will have multiple units because the application of
gasification to rice husks has not been proven in units larger than about 750kWe. The rice husk
consumption will be approximately 3.75 tonne/hr and the RHA leaving the gasifiers will be 0.675
tonne/hr. Over the course of a year of operation, the total RHA produced will be 5063 tonnes.
Typical disposal cost for RHA for transport and disposal at disposal site range from approximately
4/tonne for local disposal in developing countries where land costs are low, to 40/tonne and higher for
disposal to engineered landfills in developed countries. When disposal costs are as low as 4/tonne, the
negative cost of producing RHA which has no beneficial use would be 20,000 /year or less than 2% of
the revenue from electricity. However, when they are 40/tonne, the negative cost attributable to disposal
could be 200,000/year, almost 20% of the revenue from electricity.
One solution that has been considered for removing carbon from RHA is to use a fluidized bubbling bed
incinerator that would burn off the residual carbon in the RHA. A bubbling bed incinerator is estimated to
have a capital cost of 250,000. Assuming that operating costs are no more than the costs to operate the
basic power plant and allowing for maintenance costs of about 4% of capital cost, the annual maintenance
cost would be 10,000.
The application of this type of unit could reduce the RHA carbon content to below 7%. This would
eliminate a disposal cost 20,000 (developing country) to 200,000 (developed country). Allowing for
the maintenance costs, the potential benefit from installing the fluidized bed boiler could be 10,000/year
(developing country) to 290,000/year (developed country). Based on the additional capital cost of
250,000, the number of years to recover this amount could be 25 years (developing country) to one year
(developed country).
The above suggests that in developing countries, where sites for RHA disposal are low cost, treating RHA
from gasifiers to reduce residual carbon content is unlikely to be attractive. In developed countries, where
disposal costs are high, such treatment of ash could be attractive provided there is a beneficial use for
RHA with below 7% residual carbon exists.
b. RHA with significant quantity of crystalline silica
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Combustion of rice husks, typically in stoker fired boilers, where the ash experiences sustained
temperature above 750C leads to a significant quantity of crystalline silica in the resultant ash. The steel
market is preferred for this type of ash.
A stoker boiler power plant designed to produce 3MWe (net) will typically consume 4.11tonne/hr rice
husk. This will result in 0.74 tonne/hr RHA. Over a full year of operation, 5550 tonnes of RHA will be
available.
The net value to the producer for RHA sold to the steel industry has been reported to fall in the range 100
to 150/tonne. Based on the mid-range value of 125/tonne, the potential revenue from producing RHA
acceptable to the steel industry is 694,000/year. This could be more then 60% of the revenue stream from
sales of electricity and is, therefore, an important commercial objective.
There are no significant additional costs needed to achieve RHA with qualities suitable for acceptance by
the steel industry. On the contrary, stoker boiler technology with over grate feeders for the fuel, and no
need to pre-grind the husks, is at the low cost end of the range of equipment choices.
It is wise to choose boiler suppliers who can demonstrate their track record in producing consistent quality
RHA for the steel industry. This could tend to limit competition and hence introduce a hidden cost in the
final price. With a typical boiler cost of about 900,000, it is clear that a premium of 10% to ensure RHA
quality would be recovered in a few months of sales of RHA.
The only other additional costs for rice husk power plant generation will be related to tests on ash samples,
a higher level of quality control and probably additional employees to handle the RHA side of the
business. Clearly, with revenue from sales of potentially 694,000/year, these costs will often be no more
than 20% of the revenue.
c. RHA with high amorphous ash content
The only technology to have achieved a good long term record in producing a high amorphous RHA uses
suspension firing of pre-ground rice husk ash. Although the ground husk material can be expected to
experience temperatures above 750C, the time at temperature seems to be insufficient to change the
amorphous ash to crystalline form.
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The cost of the boiler will be similar to a stoker fired unit of the same size. The main difference will be
that there is no need for a moving grate, but the fuel will be fed pneumatically using burners suited to fine
particulate material. The extra cost for this approach is mainly associated with husk preparation which will
require rice husk grinders.
Based on a 4.11 tonne/hr husk feed, as required for the generic 3MWe (net) plant, installed cost of
hammer mill grinders is estimated to be 186,000. In addition to the capital cost, the grinders require
considerable maintenance, including replacement screens, hammers and refurbishment of cutting plates.
Based on an annual throughput of 32,500 tonne/year, the maintenance is estimated at 35,000/year. In
addition, the hammer mills will consume electricity at an annual rate of 772,000kWh. Based on a value of
electricity of 0.08 /kWh, the value of the electricity for grinding the husk is 60,000/year.
The RHA from a plant producing predominantly amorphous ash has a net value of approximately
90/tonne (allowing 30/tonne for freight to market). On this basis the total yearly revenue from sale of
the RHA from the generic plant would be 505,000. After deducting the annual cost for maintaining the
hammermills and the value of electricity to run them, the remaining revenue is 300,000. Even allowing
for additional work related to managing the sale of the RHA, the payback time for the additional
equipment needed to produce amorphous RHA will be less than six months.
Based on the above, the best choice would seem to be to produce RHA for the steel industry as this has the
best returns. However, growth in the market for RHA to the steel market is limited. Growth in the market
for RHA in the cement industry is potentially very large. For this reason, a new entrant to the marketplace
may prefer to target the somewhat less high returns but better longer term prospects of the cement market.
d. Potential to earn carbon credits
The Kyoto Protocol is part of the UNs Framework Convention on Climate Change and has set an agenda
for reducing global greenhouse gas emissions. If CO2 emissions can be shown and verified to be reduced
due to different practices, then Certified Emission Reductions (CERs) can be generated.
If RHA is used in concrete manufacture as a cement substitute then there is the potential to earn CERs.
Cement manufacturing is a major source of greenhouse gas emissions, accounting for approximately 7%
to 8% of CO2 globally.
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There is an emerging market globally for CERs, with current prices around US$5/tonne of CO2. It is hard
to predict the size and future prices within the market, but using RHA as a cement substitute can generate
CERs, and one company (Alchemix) has already investigated selling these on the international market.
The cement industry is reducing its CO2 emissions by improving manufacturing processes, concentrating
more production in the most efficient plants and using wastes productively as alternative fuels in the
cement kiln. Despite this, for every tonne of cement produced, roughly 0.75 tonnes of CO2 (greenhouse
gas) is released by the burning fuel, and an additional 0.5 tonnes of CO2 is released in the chemical
reaction that changes raw material to clinker (calcination).
The potential to earn CERs comes primarily from substituting Portland cement with RHA. There are other
environmental benefits of substituting Portland cement with RHA. The need for quarrying of primary raw
materials is reduced, and overall reductions in emissions of dust, CO2 and acid gases are attained.
The World Bank Prototype Carbon Fund provides examples of acceptable CERs from substituting
Portland Cement. Their guidelines have been adapted to show the potential income from CERs for the
generic 3MW rice husk to energy power plant used for the Cost Benefit Analysis.
A 3MW suspension fired boiler plant would typically produce 5550 tonnes annually of RHA. Assuming
50% of RHA produced is sold for cement substitution:
Emission reductions from substitution of Portland cement are calculated as totalling 1.25 tonnes of CO2
per tonne of cement substituted, derived as follows:
0.75 tonnes of CO2 per tonne of cement from energy use

0.50 tonnes of CO2 per tonne of cement from calcinating limestone
Thus the total annual emission reduction for cement with RHA substitution in cement is:
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Using estimates of approximately US$5/tonne of CO2, this could provide an additional annual income
stream of US$17,345. This is not significant compared to the potential income from sales to the steel
market and to the cement market, but could make a difference in a marginal project.
5.7 Optimization and testing runs
5.7.1 Introduction
Generally, reactivity of a pozzolanic material can be favoured by increasing fineness (Mehta 1994,
Saraswathy 2007). When burning temperature exceeds 600C partially changing silica to cristobalite,
quartz and trydimite (a crystalline material), grinding is especially important. The burning of rice husk
generates a significant volume of RHA that commonly ends up being dumped, blemishing the
environmental footprint of the rice industry. Given that rice husk comprises approximately 20% of the
unrefined rice and that RHA is 18% of rice husk, it is estimated that the total quantity of RHA generated
globally is close to 21 million tons per year. It has been demonstrated that RHA exhibits significant
pozzolanic potential; however the way in which the material develops its potential is largely influenced by
inherent factors, principally fineness and reactive silica (Mehta 1978, Mehta 1992, Malhotra and Mehta
1996, Agarwal 2006).
The study presented herein, examines the potential of a Greek rice industrys treated RHA where two
types were considered differing in reactive silica content and then fineness, in order to better understand
the nature of this stream. Fineness levels were kept, for one RHA type, first at a regular level and then at a
significantly lower level than those reported in the literature, in an effort to assess the reactivity of the
material as a function of grinding. RHA was added in mortar systems and then in concrete and factors like
strength and durability characteristics were determined to conclude on the potential of the local by-
product.
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5.7.2 Testing program
In a first study, the cement replacement considered was 10% and 15% with two different types of RHA
obtained from a Greek rice industry, named A (Agrinio) and (Thessaloniki). Mortars with 10% and 15%
cement (CEM I) replacement with each RHA were produced, as well as a silica fume mortar with 10%
cement replacement by commercial silica fume. All mortars with the same water/binder ratio were dosed
with superplasticizer in order to present equivalent workability. Specimens were tested for strength,
absorption by capillarity, chloride ion penetration, accelerated carbonation and resistivity. In the first
study, the fineness of RHA presented a mean particle diameter much greater than cement (65-70 m for
RHA in comparison to cement of 20 m). In a second study, RHA (type A) was ground very finely (with
mean particle size of 6m) and the cement replacement was 10 and 20%.
a. Materials
Materials used to produce mortar were tap water, CEM I 42,5 R type of cement, commercially available
silica fume and the two experimental types of rice husk ash A and , superplasticizer and standard CEN
sand. Particle size distribution curves of RHA and cement and SEM photos of RHA are shown in Fig 5.7
Chemical analyses are shown in Table 5.10 and compared to results by other authors.
Table 5.10 Chemical analysis for cement and RHA A and RHA and results for RHA by other authors
(Umamaheswaran and Batra 2008, Mehta 1994).
cement RHA A RHA A RHA RHA RHA RHA
Mehta
Umamaheswaran and
IETCC supplier IETCC supplier Batra 2008 1994
LOI [%] 2,85 6,34 - 6,30 0,80 3-18
total SiO2 [%] 20,41 89,05 88 - 98 86,50 88 - 98 93,52 80-95
reactive SiO2 [%] 81,43 - 78,64 -
Al2O3 [%] 4,74 1,73 <1 2,70 <1 0,01
Fe2O3 [%] 3,08 1,31 - 0,00 - 0,51
CaO [%] 62,28 3,05 <1 4,40 <1 0,68
MgO [%] 1,90 2,15 - 1,97 -
free CaO [%] 1,01 0,46 - 0,0 -
K2O [%] - <1 - <1 1-2
Reactive SiO2 determined by EN -197-1
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RHA A RHA A 2000
RHA RHA 2000
A CEM
d(0,1) 15,63 17,29 2,43
d(0,5) 65,93 70,46 19,91
d(0,9) 206,56 19,91 55,76
Cement CEMI 42,5R

Figure 5.7 Particle size distribution curves of RHA (non-ground) and cement and SEM photos of RHA
b. Mixture proportions and workability
Mortar specimens according to mixture proportions shown in Table 5.11 were produced according to NP
EN 196-1 (1996) after assessing workability. Workability was measured following the procedure
described in ASTM C230 (2003) and ASTM 1437 (2001). Control mortar (CTL) workability was set as
target workability and superplasticizer added so as to obtain equivalent workability (10mm) for all types
of mortar.
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Table 5.11 Mixture proportions and workability.
CTL SF10% A10% A15% 10% 15%

sand (g) 1350 1350 1350 1350 1350 1350
Cement (g) 450 405 405 382,5 405 382,5
ash (g) 0 45 45 67,5 45 67,5
water (g) 225 225 225 225 225 225
Superplasticizer (g) 0 3.4 1.2 2.2 1.2 2.2
workability 210.2 210.1 204.4 209.6 203.3 206.1
c. Strength
Mortar strength was determined at 7, 28 and 90 days, following the standard procedure described in NP
EN 196-1 (1996).
d. Absorption by capillarity
Transport properties of the concrete surface, which play a major role in durability of reinforced concrete,
are controlled by three mechanisms; namely, capillary absorption, permeability, and diffusion (Neville
1998). Usually, concrete that is more resistant to the ingress of aggressive agents (water or carried ions,
oxygen, and carbon dioxide) will be more durable. In the present study water absorption by capillarity,
chloride ion migration, resistivity, and accelerated carbonation tests were carried out to assess durability.
To consider the ability of the concrete surface to absorb water by capillary suction, the RILEM TC116-
PCD (1999) recommendation was adopted as a basis. The moulded side faces of 100 mm diameter and 50
mm height cylindrical specimens were tested, instead of the moulded bottom face of 150 mm cube
specimens used in the RILEM recommendation. The 56 (instead of 28) days old standard-cured (water at
20C) specimens were allowed to dry in a ventilated heater at 40C until constant mass was achieved.
After cooling to 20C, the specimens were put on rods in a shallow bath of water at 20C, approximately 3
mm deep. The uptake of water by capillary absorption was measured through the weight gain of each
specimen at time intervals until 4-1/2 h of contact with water. The absorption of water into concrete under
capillary action is dependent on the square-root of time and may be modeled as (Hall 1989):
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A a 0 St 0.5 (5.7)
where, A (mg/mm2) is the water absorption by unit area since the time the specimen was dipped in the
shallow bath; S (mg/(mm2min.0.5) is the sorptivity of the material; t is the elapsed time in minutes, and
a0 (mg/mm2) is the water initially absorbed by pores in contact with water. Testing each specimen led to
average (of 3) sorptivity results with correlation coefficients (R) over 0.978.
e. Chloride ion penetration
Chloride ion penetration was assessed by the Luping method, which is a non-steady state migration
method based on a theoretical relation between diffusion and migration. The method enables the
calculation of the apparent chloride diffusion coefficient (Dns) from an accelerated test (NT BUILD 492
1999). It is based on measuring the depth of colour change of a silver nitrate solution sprayed on the
specimens previously submitted to a migration test. Specimens (100 mm diameter by 50 mm height) were
submitted to an electrical current corresponding to a potential difference, in this case, of 30 V, during 24
h. Chloride ions are forced to migrate out of a NaCl solution subjected to a negative charge at the surface
of the specimen, through the concrete into a NaOH solution maintained at a positive potential at the
opposite surface of the specimen. The specimens are then split open, sprayed with nitrate solution and the
chloride penetration depth (xd) is measured in order to enable calculation of the apparent diffusion
coefficient (Dns) (Eq. 5.9).
0.0239 ( 273 T) L ( 273 T ) Lx d

D ns x d 0.0238 (5.9)
(U 2) t U 2

-12
where Dns is the non-steady-state migration coefficient (10 m2/s), U is the absolute value of the
applied voltage (V), T is the average value of the initial and final temperatures in the anodic solution (C),
L is the thickness of the specimen, usually 50 mm, xd is the average value of measured chloride
penetration depth (mm), and t is the testing period (h).
f. Resistivity
Concrete resistivity is another parameter that contributes to durability assessment. When pores are
saturated, electric current flows more easily, depending on the pore structure. Prior to the chloride
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migration test described above, specimens are pre-saturated. Therefore, when current is imposed during
the test it is possible to evaluate resistivity, Eq. (5.10), in saturated conditions to compare different types
of concrete, in this case, mortar.
A VA
R (5.10)
L LI
where R is the electric resistance, ( - Ohm), I, current (A), V, voltage (V), , electric resistivity (.m),
L, length (m), and A (m2), the area of the test specimen across which current passes.
g. Carbonation
Accelerated carbonation tests were carried out following the procedure described in LNEC E391 [1993],
using a chamber with 5% carbon dioxide and relative humidity (RH) of approximately 65%. 4040160
mm test specimens of each mortar type were kept in the chamber for two months, after 28 day curing in
water at 20C. A slice from each test specimen was sawed off and sprayed with phenolphthalein solution,
enabling the measurement of the carbonation depths.
5.7.3 Test results & discussion
Strength results at 7, 28 and 90 days, sorptivity results, resistance to chloride penetration, resistivity results
at 56 days and carbonation results of each mortar type, are shown in Table 5.12. All these results refer to
the regular ground form of RHA. Both types of RHA mortar with 10% and 15% cement replacement
performed worse than the control mortar regarding strength, resistance to chloride penetration and
carbonation resistance. Although a similar reduction, on average, in compressive strength was noticed at
28 and 90 days (10 % and 9% respectively) for all the RHA mortar samples, samples incorporating 15%
RHA produced much higher carbonation depths (89% increase) than those incorporating 10% (17 % to 33
% increase).
In terms of resistivity, samples incorporating 15% RHA produced an increase compared to control (9%
and 15% for RHA type A and respectively), while on samples with 10% RHA the resistivity was
decreased (16% maximum decrease for RHA type ). In terms of sorptivity, performance increased with
replacement percentage (a 65% increase was noticed on samples incorporating 15% RHA type ).
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Table 5.12 Mechanical and durability test results and enhancement by the use of RHA (regular
ground).
Results and Enhancement CTL A10% A15% 10% 15% SF10%

Rslt. 38,7 37,1 37,5 38,6 37,1 48,7
7 days [Mpa]
Enh. -4% -3% 0% -4% 26%
Rslt. 48,0 42,5 42,9 44,6 42,6 58,8
28 days [Mpa]
Enh. -11% -11% -7% -11% 22%
Rslt. 53,3 48,4 49,0 49,1 47,7 58,0
90 days [Mpa]
Enh. -9% -8% -8% -11% 9%
Rslt. 0,1510 0,1233 0,0653 0,1023 0,0533 0,0883
S [mg/(mm2.min1/2)]
Enh. 18% 57% 32% 65% 42%
Rslt. 15,31 16,32 17,62 17,24 16,59 2,44
Dns [10-12 m2/s]
Enh. -7% -15% -13% -8% 84%
Rslt. 3,0 3,5 5,7 4,0 5,7 4,8
Carbonation [mm]
Enh. -17% -89% -33% -89% -61%
Rslt. 53,7 48,6 58,4 44,9 61,8 279,5
Resistivity [.m]
Enh. -9% 9% -16% 15% 420%
Enhancement (Enh.)=(Rslt.RHA-Rslt.CTL)/Rslt.CTL
In Table 5.13, strength and accelerated chloride test results on concrete are given for the second study,
where RHA (type A) was ground very finely to obtain SRHA (Fig. 5.8) and used as 10 and 20% cement
replacement in concrete.
d(0,1): 1,41m
d(0,5): 4,85m
d(0,9): 15,43m
Figure 5.8 Particle size distribution curve of SRHA
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Table 5.13 Mechanical test results, left and electric charge, right, in concrete with superfine RHA.
Charge passed Permeability Class

10% 20%
Control SRHA SRHA [Coulombs] [ASTM]
7d 38.7 39.2 38.9 Control 2719 Moderate
28 d 48.0 51.2 50.2 10% SRHA 2569 Moderate
20% SRHA 864 Very Low
At 7 days the compressive strength proved to be similar to control samples (1% increase for both 10% and
20% levels of RHA), while at 28 days strength was slightly increased up to 7% for samples incorporating
10% RHA. Superfine RHA performs better than cement, even for 20% replacement. In this second study
the chloride resistance of mortar incorporating SRHA was also evaluated, using the ASTM accelerated
penetration test method. The samples before testing, were immersed for a period of 55 days in saturated
Ca(OH)2 solution. This period of time is more than adequate for a sufficient level of cement hydration and
pozzolanic reactions of the ash used, as previously shown. The overall excellent behavior of the samples
tested (in comparison to control) is given in Table 5.13, right, where the electric charge passed through the
samples is given for both levels of SRHA used.
It is obvious that the mechanical grinding led to the development of smaller grain sizes than those of
cement. It is generally acceptable that, at concrete level, the small grain sizes of ash strengthen (through
the filler effect) packing among aggregates (especially in the case of fine aggregates) and cement grains.
This is further enhanced with pozzolanic ash, reducing in this way the overall porosity (hence the
permeability) of the final product. This is confirmed by results obtained according to the official
classification by ASTM C1202 (see Table 5.13, right), where mortar incorporating SRHA exhibits low
permeability to chloride ingress, in contrast to conventional mortar where permeability observed is of
medium level.
5.7.4 Discussion and further suggestions
The work presented in this study, examines the potential use of a Greek rice indusrtys upgraded RHA
where two types were considered differing in reactive silica and then fineness so as to better understand
the nature of this waste stream. Fineness levels were kept, for one RHA type, first at a regular level and
then at a significantly lower level than those reported in literature, in an effort to assess the reactivity of
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the material as a function of grinding. RHA was added in mortar systems and factors like strength and
durability characteristics were determined to conclude on the potential of the local by-product.
In the first study, cement replacement considered was 10 and 15% with the two different types of
RHA, with regular grinding. Both types of RHA mortar with 10 and 15% cement replacement
performed worse than control mortar in regard to strength, resistance to chloride penetration and
carbonation resistance. Performance in terms of resistivity was similar to control and in terms of
sorptivity, performance increased with replacement percentage. Unsatisfactory results were explained
by insufficient fineness evaluated by laser particle distribution on the RHA samples.
A second study involving cement replacement with 10 and 20% of RHA ground very finely, led to
equivalent or better results compared to control concrete in terms of strength but, principally, chloride
resistance was dramatically increased thus leading to the conclusion that fineness is a key issue in
terms of RHA use as a cement replacement material.
As cement industry contributes significantly to global CO2 emissions, making cement production greener
is currently a very urgent challenge. Reducing the rate of clinker production by using mineral
replacements, i.e., additions or supplementary cementing materials such as RHA with enhanced reactivity,
contributes to greener concrete and thus sustainable construction.
Although the above recent results showed that RHA is a good pozzolanic material i.e. hydraulic
character may result when moisture is present - and also building materials acquire a number of desirable
properties because of it (water demand reduction in comparison to silica fume, increased resistance to
alkali, reduced erosion due to improved packing, etc.), this Greek product still faces two challenges in
order to increase its exploitation in the building sector:
its limited availability
its reduced activity - in relation to silica fume
Because of the above, there is limited interest of the domestic cement industry for the Greek RHA (as this
industry is now into additives with substantial and continuous supply, and moreover due to current
economical crisis). The apparent abandoning of RHA use in composite cements leads to the
implementation of "special" applications or products, e.g. RHA use in special mortars (e.g. repair), or to
concrete with specific requirements (e.g. "gunite") at rates that are allowed by the Greek concrete norms.
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For the above solutions to be realistic and given that the activity of the Greek RHA is not proportional to
the activity of additives such as silica fume (k = 3) or metakaolin (k = 2.5), the k of the Greek RHA needs
to be increased. Thus, ways for its activation should be further sought. This combined with the inherent
property of RHA to demand less water for the same workable and the proved durability in time, can lead
to an end product of high value that will be used almost exclusively in the dry construction.
The two features of RHA that need to be affected in order to activate it are: (a) its rich siliceous structure
and (b) its fineness. If any of these (or both) are affected significant changes in the activity of RHA may
be caused. Previous experience with less active materials (eg fly ash, slag, etc.) has shown that such
changes can be catalytic and financially advantageous.
The following activation methods are proposed to be studied:
Ultra-fine jet milling: the mechanical activation is tested by grinding to a special air jet mill. This does
not work like the conventional sphere mill, but works with collision with air flow that ensure collisions of
RHA and lead (using embedded splitter) in very fine particles. Given the extreme sensitivity of RHA to
fineness change, it is estimated that ultra-fine jet milling will activate RHA more than it was achieved
with the sphere or vibrated mill.
Selective fractionation: refers to the processing of the coarse fraction (e.g. 45 mm) of RHA. We take
advantage of the expected enrichment in active SiO2 to a higher quality pozzolan than the original. Sieving
and grinding is required (in order not to lose the filler effect of RHA) while attention is given to factors
such as unburned carbon (LOI), which also is expected in coarse fractions. Similar experiments in the
Greek fly ashes gave impressive results by demonstrating higher strength (mostly final)> 10-15%.
Grinding in the presence of grinding aid/strength enhancer: The separate grinding of pozzolans is a
trend in many European countries. Usually grinding improvers are used when grinding pozzolans and
clinker together. However, research has progressed a lot and now there are additives that can help the
grinding and also unleash the potential of pozzolans (strength enhancers). Similar experiments with
slag have shown that the individual components of these enhancers (usually a mixture of organic
compounds) intervene in the ingredients of pozzolana and activate them. In the case of the RHA this is a
new field, but given the mineralogy of the material a number of additional auxiliaries can be studied. It is
also a fact that the separate grinding of RHA and its subsequent integration into cement is expected to give
better results than grinding it together with clinker.
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Cooling rate: a key factor for the percentage of amorphism (and thus activity) of RHA. Generally, the
more rapid cooling takes place the higher level of amorphism of the material is expected. Along with the
investigation at laboratory scale (simulation of production conditions and application of different cooling
rates from the slowest to very sudden water extinction - and 1-2 intermediate), the extension to an
industrial level plant is proposed as long as there is such a possibility for the Greek rice industry.
5.8 Environmental benefits
Under the scope of the present study, an evaluation of RHA, alone or as mixes with other ashes, as Type II
additives on CEM I type of cement, and their effects in terms of their performance in carbonation and
chloride exposure, for a service life of 50 years, in addition to their environmental output is carried out.
The overall aim is to portray the basis for the previously mentioned balanced approach between
sustainability and durability of reinforced concrete structures (optimum solution, Chapter 3).
5.8.1 Estimation of concrete service life
The effect of cement type on the overall durability design of concrete exposed to corrosive environments,
due to carbonation and chloride diffusion, is briefly presented in this section for reasons of integrity
(despite it has been presented in Chapter 2). As durability indicators, calculation of the carbon dioxide
penetration front, for a period of 50 years, was used for carbonation exposure, while under chloride
ingress, the estimation of the adequate concrete cover needed to sustain a service life of 50 years was
calculated.
The service-life, and compressive strength, evaluation were made using a software tool (EUCON), based
on proven predictive models (according to performance-related methods for assessing durability)
developed and validated elsewhere (Papadakis 1999, Papadakis and Efstathiou 2005), for the estimation of
concrete service life when designing for durability under harsh environments. Concrete service life is
reliably predicted using fundamental mathematical models that simulate the basic deterioration
mechanisms of reinforced concrete (carbonation, chloride penetration). Principles of chemical and
material engineering have been applied to model the physicochemical processes leading to concrete
carbonation, as well as the processes of chloride diffusion in the aqueous phase of pores, their absorption
and binding in the solid phase of concrete and their desorption.
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A constant volume unit (1 m3) of concrete was chosen as a common basis. When an SCM (or a mixture of
SCM) was added to this unit, then an equal volume of another component, either cement or aggregate, was
removed in order to keep the same total volume and the common comparison basis. A typical CEM I mix,
water cured for 28 days (as it is assumed by the proven predictive model used) was selected as the
reference type of cement (w/c: 0.5, cement content 300 kg/m3, 31.5 mm crushed aggregates, no additives,
no admixtures). Several mix design configurations were considered, where each time addition of FA, RHA
and a mixture of 50 % FA and 50 % RHA, (as Type II additives) took place, as cement and as aggregate
replacement. 10, 20 and 30 % replacement levels of the control cement mass were chosen, with the water
content (kg/m3) kept constant for all specimens. The mix design configuration and the results observed are
given in Table 5.14.
Table 5.14 Mix design and durability indicators.*
SCM SCM
C W w/c A FA RHA fcu fcu rFA rRHA Xc xc C50 C50
type (%)
0 300 150 0.5 1925 - - 44.6 - - - 19.6 - 29 -
FA As aggregate replacement
10 300 150 0.50 1896 30 - 51.4 15.3 1 - 15.9 -19 19 -34.5
20 300 150 0.50 1866 60 - 58.0 30.0 1 - 12.4 -37 11 -62.1
30 300 150 0.50 1837 90 - 64.4 44.4 1 - 9.8 -50 5 -82.8
As cement replacement
-10 270 150 0.56 1920 30 - 45.8 2.69 1 - 21.3 8.7 25 -13.8
-20 240 150 0.63 1916 60 - 46.9 5.16 1 - 23.3 18.9 21 -27.6
-30 210 150 0.71 1911 90 - 48.0 7.62 1 - 25.5 30 17 -41.1
RHA As aggregate replacement
10 300 150 0.5 1890 - 30 51.4 15.3 - 1 17.7 -9.7 11 -62.1
20 300 150 0.5 1856 - 60 56.3 26.2 - 0.87 16.1 -18 3 -89.7
30 300 150 0.5 1821 - 90 56.3 26.2 - 0.58 15 -23 3 -89.7
-10 270 150 0.556 1915 - 30 45.8 2.69 - 1 23.4 19.4 17 -41.4
-20 240 150 0.625 1905 - 60 42.8 -4.04 - 0.7 28.2 43.8 13 -55.2
-30 210 150 0.714 1895 - 90 35.9 -19.5 - 0.41 34.4 75.5 23 -20.7
As aggregate replacement
10 300 150 0.5 1893 15 15 51.4 15.3 1 1 16.6 -15 15 -48.3
20 300 150 0.5 1861 30 30 58 30.0 1 1 14.4 -26 5 -82.8
30 300 150 0.5 1829 45 45 59.1 32.5 0,45 1 14.1 -28 3 -89.7
FA+RHA As cement replacement
-10 270 150 0.556 1918 15 15 45.8 2.69 1 1 22.1 12.8 21 -27.6
-20 240 150 0.625 1910 30 30 46.9 5.16 1 1 25.4 29.6 13 -55.2
-30 210 150 0.714 1903 45 45 35.9 -19.5 0 0.82 35.1 79,1 23 -20.7
* C, cement content (kg/m3), W, water content (kg/m3), W/C water/cement ratio, FA fly ash content (kg/m3) RHA rice husk ash
content (kg/m3), fc concrete compressive strength (MPa), xc carbonation depth (mm), C50 adequate concrete cover needed to
sustain chloride exposure for 50 years (mm).
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Overall it was seen that when SCM were used for aggregate replacement, the carbonation depth was
decreased compared to the control mix. Incorporation of FA in CEM I type of cement, produced a better
performance under carbonation exposure than the other SCM types and mixtures used. Addition of 30% of
FA reduced the carbonation depth by 50%, compared to 23.5% and 28.1% reductions, when RHA and
their mixture (50% RHA and 50% FA) were used respectively. In the case where SCM were used as
cement replacement materials, the carbonation depth was increased, with the increasing content of every
type of SCM used.
As far as chloride exposure is concerned, specimens incorporating SCM whether aggregate or cement was
substituted, produced smaller concrete cover values needed to sustain chloride exposure for a service life
of 50 years, compared to control. RHA proved to inhibit chloride diffusion more efficiently than FA. A
89.7% reduction of the previously mentioned adequate concrete cover was noticed, compared to 82.8%
reduction when FA was used, for a 30% content of SCM.
Overall utilisation of SCM in concrete mix design produced considerable gains in the 28 days concrete
compressive strength. Incorporation of FA produced an increase of 44.4% (from 44.6 MPa to 64.4 MPa)
compared to the 26.2% and 32.5% increases when RHA and the RHA-FA mixture were used,
respectively.
5.8.2 Environmental impact of concrete
It was previously mentioned that in producing concrete the main emissions to air are associated with
cement manufacturing. However, other concrete constituents also contribute in that sense. In general, it
can be said that the CO2 emissions from concrete production are the summation of the emissions from, the
chemical conversion process in clinker production (during cement manufacturing), from the energy
consumption due to fossil fuel combustion (also during cement manufacturing), from the electrical energy
required for the grinding of any additive materials and from the energy required (in terms of fuel
consumption) for the transportation of the raw materials and of the final product. A more precise
estimation of the environmental footprint (environmental factors) of each individual concrete component,
based on the literature and on data derived from a Greek cement manufacturing company, is presented in
this section. The overall environmental footprint of concrete (Econc) can be calculated as:
Econc = CEc + RER + FEF + AEA + WEW + DED (5.11)
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J.G. Tapali
C, R, F, A, W, D: are the contents (in kg / m3 of concrete) of cement, rice husk ash, fly ash,
aggregate, water and admixtures, respectively, and
EC, ER, EF, EA, EW, ED: the environmental cost (in kg of CO2 / kg of cement) of cement, rice husk
ash, fly ash, aggregates, water, admixtures, respectively.
For the calculation of the environmental cost of the individual concrete components the following were
taken under consideration.
In terms of cement, according to the literature, the CO2 emissions associated with cement production vary
from 700 to 1000 kg CO2/kg cement (Flower et al. 2007). According to Hoeing et al. (2010) 0.65-0.92 kg
of CO2 is produced for per kg cement produced based on a cement plant with a modern technology and
equipment. The CO2 emission for cement Type I is approximately 800 g/kg cement, less for the other
cement types with lower clinker contents (Josaa et al. 2004).
In this study a more precise estimation was made using operational and production data from the Greek
cement-manufacturing company. By taking under consideration the chemical equation of incomplete
combustion of coal (Eq. 2), where 94 kcal/mol of energy is produced (Q), since it is an exothermic
reaction, the amount of CO2 produced from energy consumption of 1KWh is calculated as 0.404 kg (1 cal
is equal to 1.162 10-6 kWh, hence 94 kcal equal to 0.109 KWh producing 44 g of CO2).
C + O2 CO2 + Q (5.12)
By taking into account data as, the amount of cement produced (1,700,000 tn/year), the electrical energy
required (500,000 kWh/day) the level of CO2 emissions measured (3,801,000 kg/day) and the total days of
operation per year (335) the total CO2 emissions were calculated to be in the range of 1,341,005 t/year.
Hence in order to produce 1 t of cement 0.79 tn of CO2 are emitted into the atmosphere. In addition to the
later, the derived CO2 emissions from transportation should be added. Considering that on average 2.74 kg
of CO2 is emitted per litre of fuel, using vehicle transport, and that fuel consumption is estimated to be 1 lt
/ 3 km for 5 tn of raw materials, the overall emissions arise from transportation are estimated to be 0.183
kg / km / t of raw material (GHG Protocol 2001).
In order to extract, process and grind aggregates the overall CO2 emissions are estimated to be 5.96 kg / t
of aggregates (considering that 2.53 kWh are required for the production of 1 tone of aggregates and that 9
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lt of fuel are required for the transportation of a 5 tones shipment, resulting in 4.94 kg of CO2 / t of
aggregates).
When fly ash is used as a secondary cementing material, since it is a by-product of coal burning in
electrical power stations, the emissions associated with power generation are not considered of being part
of the environmental burden of fly ash. A small amount of energy required for the grinding of the raw
material into very fine powder and for its transportation, are the only sources of greenhouse gasses.
According to the literature (Integrated Pollution Prevention and Control (IPPC) 2010, U.S. Environmental
Protection Agency 2008) the previously mentioned energy requirement is estimated to be in the order of
20 kWh per tone of fly ash produced, hence 8.06 kg of CO2 per tone of fly ash (emissions from
transportation, similar to cement transportation, should also be added).
Table 5.15 Mix design and environmental indicators.
SCM SCM EC
C W w/c A FA RHA Xc C50 EC PC
type (%) (%)
0 300 150 0.5 1925 - - 19.6 29 311.47 - 44.76
FA As aggregate replacement
10 300 150 0.50 1896 30 - 15.9 19 311.56 - 45.07
20 300 150 0.50 1866 60 - 12.4 11 311.64 - 45.38
30 300 150 0.50 1837 90 - 9.8 5 311.72 - 45.70
-10 270 150 0.56 1920 30 - 21.3 25 281.70 -9.6 42.66
-20 240 150 0.63 1916 60 - 23.3 21 251.94 -19.1 40.56
-30 210 150 0.71 1911 90 - 25.5 17 222.16 -28.7 38.47
RHA As aggregate replacement
10 300 150 0.5 1890 - 30 17.7 11 311,30 - 46.96
20 300 150 0.5 1856 - 60 16.1 3 311.13 - 49.17
30 300 150 0.5 1821 - 90 15 3 310.95 - 51.37
-10 270 150 0.556 1915 - 30 23.4 17 281.45 -9.7 44.55
-20 240 150 0.625 1905 - 60 28.2 13 251.42 -19.3 44.34
-30 210 150 0.714 1895 - 90 34.4 23 221.39 -28.9 44.14
FA + RHA As aggregate replacement

10 300 150 0.5 1893 15 15 16.6 15 311.43 - 46.02
20 300 150 0.5 1861 30 30 14.4 5 311.38 - 47.28
30 300 150 0.5 1829 45 45 14.1 3 311.34 - 48.54
-10 270 150 0.556 1918 15 15 22.1 21 281.58 -9.6 43.61
-20 240 150 0.625 1910 30 30 25.4 13 251.67 -19.2 42.45
-30 210 150 0.714 1903 45 45 35.1 23 221.78 -28.8 41.30
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J.G. Tapali
In the case of rice husk ash, since it is available from limited regions on European level, the related
emissions arise from the amounts of energy required for the controlled burning of rice husk, for the
grinding of the raw material into very fine powder and for its transportation. They can be safely assumed
to be twice of those of fly ash.
As far as water is concerned, the only source of emissions arises from the electrical energy required to
pump the water, which in this study is considered to be negligible. The total volume of admixtures added
in a concrete mix is usually less than two litres per cubic metre of concrete. In addition, the CO2 emissions
generated from admixtures are very small (2.2 53 x 10-3 kg CO2-e/l admixtures). Therefore, the
environmental footprint of admixtures can be ignored. Since no admixtures were used on the mix design
of the different concrete configurations used in this study, the environmental impact of admixtures is
ignored. In this way, based on the proportions of the concrete constituent materials used (Table 5.14) and
on the environmental factors, as derived above, the overall environmental cost of concrete was calculated
(Table 5.15). For reasons of comparison, the durability indicators (carbonation depth xc and adequate
concrete cover to sustain chloride exposure for 50 years c50) as well as, an estimation of the economical
cost of each mix design used, based on the individual prices of the raw materials are also given in Table
5.15.
A first observation is that utilization of SCM as aggregate replacements did not change significantly the
environmental output of concrete, however, when SCM were used as cement replacements, considerable
reductions of up to 28.9 % of the environmental footprint were noticed. A comparative assessment of
every durability, environmental and economical cost indicators, calculated in this study, for every type
of SCM used is given in Figure 5.9. In this way, the reduction of environmental cost observed can be
weighted against the durability and service life indicators (especially for chloride exposure) calculated.
Overall, the mixture of FA with RHA produced the best balanced behavior, followed by the case when
only FA was incorporated in the concrete mix.
A 20 % addition of RHA and FA increased the concrete compressive strength by 5.2 % (same increase as
in the case of FA) and produced a 55.2 % reduction of the adequate concrete cover needed to sustain a
chloride free structure for 50 years (compared to a 27.6 % when FA was used) resulting also in a 19.2 %
reduction of the overall associated CO2 emissions. However, at higher rates of cement replacement (30 %)
FA proved to be more effective resulting in 7.6 % increase of concrete compressive strength and to 20.7 %
and 28.7 % reductions of the concrete cover in terms of chloride attack and of the associated
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environmental cost. At this rate of cement replacement RHA and RHA/FA mixture gave a lesser
performance than FA. The reasons for such a behavior are analyzed in the following section.
5.8.3 Discussion and conclusions
A thorough design of reinforced concrete structures must be the combination of an integrated study and a
techno-economic optimization. Economical, environmental and technical parameters must be taken into
account for the definition of the best solution. On this note, the aim of this study is to evaluate in terms of
service life and environmental cost indicators, the effect of different supplementary cementing by-
products. A software package based on proven, verified predictive models was used for the evaluation. As
far as carbonation exposure is concerned, carbonation depth was estimated for a period of 50 years. In
terms of chloride ingress, the adequate concrete cover needed to sustain that ingress for a period of also 50
years was estimated. The environmental footprint of concrete was calculated, based on the estimation of
the range of CO2 emissions of each individual concrete component, using data from the literature and from
a cement production company.
The results of this study, as far as the service life estimation is concerned, showed that FA, RHA and its
combination reduced considerably the carbonation depth values, compared to the control mix when used
as aggregate replacements, an observation also reached by other researchers (Khunthingkeaw et al. 2006,
Valcuende and Parra 2010). However, when the above mentioned materials were used as cement
replacements, larger carbonation depths were produced, compared to control. The explanation for such a
behaviour lays in the way these materials were incorporated into the mix. In the first case, the total amount
of carbonatable constituents remains almost the same, resulting in decreased porosity and lower
carbonation rates (Papadakis 2000). While in the second case, by reducing the cement and clinker content,
the amount of carbonatable materials is also reduced (due to the decrease in total CaO), resulting in higher
carbonation rates (Valcuende and Parra 2010). In general SCM materials (as cement replacements) proved
to be less resistant to carbonation, mainly due to their low binding capacity of CO2, caused by their
smaller concentrations of Ca(OH)2, compared to control (due to the consumption by pozzolanic reaction,
and lower cement content).
Under chloride exposure they all behaved much better than control. It has been noticed that specimens
incorporating an SCM, whether it substitutes aggregate or cement, exhibit significantly lower total
chloride content for all depths from the surface (Hosam et al. 2010). RHA, when used as additive, proved
to be most efficient in inhibiting chloride ingress (up to 20 % replacement). RHA, composed by very
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J.G. Tapali
small spherical particles, due to its ultra fineness and activity led to the formation of intense pozzolanic
reaction products (with increased chloride ion binding capacity than fly ash) within the capillary pore
spaces and as a consequence, a finer and more segmented pore system is produced (Antiohos et al. 2014,
Papadakis and Tsimas 2002). The reactivity of RHA can be attributed to its high content of non-crystalline
silica, and to its very large surface area governed by the cellular structure of the particles (Mehta 1994,
Zhang and Mlhotra 1996, Chandra 1997). When pozzolanic materials with high active silica content are
added to cement, the silica (SiO2) present in these materials reacts with free lime released during the
hydration of cement and forms additional calcium silicate hydrate (CSH) as new hydration products which
improve the mechanical properties of concrete formulation (Ganesan and Thangavel 2007). However
when all the available free lime is depleted, the pozzolanic reactions stops and the remaining levels of
silica remain inactive. Such an observation is further reinforced by the rate of the pozzolanic reaction of
RHA, which at high replacement levels drops bellow 0.8 (even bellow 0.5 when RHA is solely used).
On the contrary, when FA is used, a full pozzolanic reaction level is observed (rate of pozzolanic reaction
equal to 1) resulting in higher reductions of concrete cover able to resist a chloride attack and also in
further increases of concrete compressive strength, for higher replacement levels than when RHA is used
(30%). FA, due to its high calcium oxide content, apart of being pozzolonic active, reacts faster than the
siliceous cement replacement materials, since it contains higher amounts of aluminate-cementing
compounds (C3A, C4AF), leading to a more increased chloride ion binding capacity (Antiohos et al.
2007).
Overall, by taking under consideration the environmental and economical cost, as estimated in this study
(Table 5.15), a more complete portrait of the properties and effects of every particular mix design used
was created (Fig. 5.9). In this way and for any type of SCM used, the designer can balance its mix design
based on the properties of durability and environmental (or economical) cost (Fig. 5.10) to achieve the
best possible (optimum) solution, according to the requirements of his particular study.
CONCLUSIONS
The concrete industry is facing the challenge of providing and safeguarding a sustainable design of
buildings and structures. To achieve that, relevant environmental, financial and service life factors should
be taken under consideration.
On this note, an assessment of durability and environmental cost indicators of a concrete mix utilising
supplementary cementing by-products took place, aiming to achieve a balanced level of sustainable and
durable design (green durability). The most important finding of this study can by summarised as follows:
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70 35 35 350 70
60
Adequate concrete cover to sustain cl-
30 30 300 60
Environmental Cost (kg of CO2

emissions / m3 of concrete)
exposure for 50 years (mm)
50
25 25 250 50
Economical Cost
40 20 20 200 40
30 15 15 150 30
20 10 10 100 20
10 5 5 Substituting cement FA Substituting aggregates 50

10
0 0 0 0 0
-30 -20 -10 0 10 20 30
35 35 35 350 70
30 30 30 300 60

25 25 250 50
25
Economical Cost
200 40
20 20 20
150 30
15 15 15
10 100 20
10 10
Substituting Substituting
5 5 5 cement RHA aggregates 50 10
0 0 0 0
0
35 35 35 350 70
30 30 30 300 60

25 25 25 250 50
Economical Cost
20 200 40
20 20
150 30
15 15 15
10 100 20
10 10
Substituting Substituting
5 5 5 RHA+FA aggregates 50 10
cement
0 0 0 0
0
Figure 5.9 Durability and cost indicators for SCM mixes.
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J.G. Tapali
35 350 70
Adequate concrete cover to sustain chloride
30 300 60
(kg of CO2 / m3 of concrete)
( / m3 of concrete)
25 250 50
Economical Cost
Environmental Cost
20 200 40
15 150 30
10 100 20
5 50 10
Substituting cement Substituting aggregates
0 0 0
-15 -10 -5 0 5 10 15
Figure 5.10 Area of balanced (optimum) sustainable and durable design incorporating SCM.
The effects of the SCM materials on the behaviour of the concrete mix differ when used as aggregate
or cement replacements.
The use of SCM as an addition to a concrete mix, replacing either aggregates or cement, significantly
decreases the adequate concrete cover needed to sustain chloride exposure for a service life of 50
years.
The environmental footprint of each individual concrete component can be quickly estimated, based
on data from the literature or from production and operational data from cement-manufacturing
companies.
Utilisation of SCM as cement replacement reduces considerably the total concrete CO2 emissions.
By taking under consideration the environmental and economical cost a complete portrait of the
properties and effects of every particular mix design used, was created
RHA and FA mixture proved to be the most promising SCM material, for a replacement level up to
20%, in providing a balanced environmentally friendly durable solution (under chloride exposure).
While FA gave the most coherent overall behavior at larger replacement levels (30%).
Bearing all of the above in mind, it was shown that it is possible to achieve an adequate level of green
durability (under chloride exposure) in concrete design, in other words a balance between sustainability
and durability, by utilising SCM by-products (and mixtures) in the concrete mix. It is hoped that the
results of this study will pave the way for a more rigorous approach to be adopted by the research
community on the level of sustainability afforded by using such types of materials.
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Chapter 6. Conclusions
In the Introduction (Chapter 1), a brief description of the building sector is presented in terms of basic
characteristics, production rates, and relevance with the economy growth. The various environmental
impacts of the building sector are analyzed and grouped, whereas the potential measures, products and
techniques for reducing the environmental cost of the constructions are outlined. The interest is
focuses on concrete as the main building material. The environmental cost of each individual concrete
constituent can be estimated, based on data from the literature or from production and operational data
from building materials manufacturing companies. Therefore, it is possible to estimate the
environmental footprint of concrete and achieve an adequate level of sustainability and durability in
the design of reinforced concrete buildings and structures.
Main objective of the present Thesis is to introduce a new indicator: the environmental cost, which,
in addition to the existing characteristics or indicators connected with mechanical, durability and
economical performance, to offer a complete view able to perform an overall design optimization for
concrete structures. Moreover, as new supplementary cementing materials have been appeared, such
as biomass ashes, very efficient on concrete properties improvement, a special attention is given as
materials for reducing the environmental cost. Among them, rice husk ash is the most promising
biomass ash, deserving thus an in depth techno-economic analysis.
Service life and durability of concrete are strongly related with the environmental footprint of
constructions. It is obvious that a structure with a longer service life is less harmful to the environment
during the phase of operation. In Chapter 2, therefore the concrete durability according to the
European Standard EN 206 is first presented, then, the development of a concrete mix design is given
including the concrete constituents and, finally, the concrete service life estimation tool (EUCON) is
presented with the improvements made in the present Thesis on environmental cost assessment.
More specifically, the concept and the main principles of this software tool (EUCON, based on
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deterministic proven predictive models) for the estimation of concrete service life were presented. Its
structure is in full compliance with the European Standards for cement (EN-197) and concrete (EN-
206). Emphasis was given on the mathematical modelling of the physicochemical processes leading to
concrete deterioration (due to carbonation and chloride ingress) and their outputs. In addition the
results of a wide validation scheme implemented were presented, to further reinforce the effectiveness
of the mathematical models used.
The tool presented offers a comprehensive approach on concrete service life estimation, in terms of:
Defining the concrete mix design and the main chemical/volumetric characteristics of concrete.
Estimating the compressive strength class.
Accurately predicting the concrete service life, for carbonation and chloride exposure, by taking
under consideration the relative exposure classes and by utilising proven predictive mathematical
models of the physicochemical processes leading to such deterioration.
It should also be noted that even though service life predictions are usually made in a probabilistic
framework (to account for the many uncertainties associated with the composition, processing,
construction, curing/maintenance of reinforced concrete, etc.), based on the validity of the results
presented in this study, this particular deterministic model can serve as a basis for modeling within
such probabilistic frameworks. Supplementary cementing materials (SCM) can replace either cement
or aggregates in the concrete mix. In this way and for any type of SCM used, the designer can
balance its mix design based on the properties of durability and environmental (or economical)
cost to achieve the best possible (optimum) solution, according to the requirements of the
particular study.
In Chapter 3, trying to investigate the relationship of sustainable and durable design, a (4-step)
structured methodology was presented aiming to provide a concrete mix design with accepted strength
and service life properties, but with the minimum environmental cost. First, the concept of the
environmental cost is analysed and then it is estimated for the concrete production according to
literature and industry data. A structured methodology for concrete mix design optimization
(Integrated Design Process) is then presented in details and utilized for typical applications offering a
significant tool towards sustainable concrete constructions. Considering the increased demand for
cement and concrete, in addition to the considerable levels of CO2 emissions associated with the
cement manufacturing process, a more sustainable design of concrete mixes should be enforced.
Under this scope, utilization of industrial by-products as cement (clinker) replacement materials is a
promising solution. The main findings, as discussed in this study can be summarized as:
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The effects of the SCM materials on the behaviour of the concrete mix differ when used as
aggregate or cement replacements (in terms of service life to carbonation).
Calcareous fly ash proved to be the most promising SCM material (for up to 30%), in providing a
balanced environmentally friendly and durable solution. A further decrease in the environmental
burden (up to 45 %) was achieved, when the rate of the pozzolanic reaction dropped below 1.
By taking under consideration the calculated environmental cost of a concrete mix and the derived
strength and service life values, an area of accepted performance upon initially selected target
values (40 MPa, 50 years) was created.
In this way, a mix design incorporating a particular type of SCM can be further adjusted in achieving
an optimum sustainable and durable performance, according to the principles set in the newly imposed
relevant EN 15643 Standards. It is hoped that the results of this study will pave the way for a more
rigorous approach to be adopted by the research community on the level of sustainability afforded by
using such types of materials.
The main aim of Chapter 4 was to shed light on the specific influence of the main characteristics of
biomass ashes (new SCM) on concrete strength development and performance in chloride exposure,
exploring in this way their future utilization in cement and concrete manufacturing. Types and
evaluation methodology for biomass ashes are presented together with results and discussion on their
evaluation as concrete constituents. By investigating the efficiency of a range of biomass ashes,
identified in the literature, as cementitious materials, in terms of efficiency factors for concrete
strength and chloride penetration, it can be concluded that:
Variations in the operating conditions (temperature of combustion, technology used) and

source of the biomass can influence to a great extend the chemical characteristics of the
biomass ashes, even of the same group.
High SiO2 content in the biomass ash, does not automatically implies an effective pozzolanic
material with a high efficiency factor.
It appears that after certain percentages in the concentration of the ash in Al2O3, Fe2O3 and
CaO, even for high SiO2 content, high level of fineness, and low values of LOI, the derived
efficiency factors drop below 1.0.
Biomass ashes (except wood related aches) from a variety of agro-industrial by products can
be used as cement replacement materials with beneficial results in strength development and
performance in chloride penetration.
Concrete impermeability properties are considerably improved due to pore refinement in
biomass ash blended concretes compared to control concrete.
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J.G. Tapali
Utilization of RHA drastically reduced the Coulomb values and subsequently the
corresponding chloride penetration.
Overall, utilization of agro-industrial by-products for biomass ash production can be a valid
source of a future pozzolanic material in concrete production.
It is hoped that the results of this study can be used for in depth evaluation of a wider range of biomass
ashes on cement and concrete production towards a sustainable construction.
Focusing on rice husk ash (RHA) - a main biomass ash and efficient pozzolanic material, provided its
amorphous and fine state techno-economical aspects are analyzed in detail in Chapter 5. A technical
and financial study and a preliminary design for the industrial production of the RHA-derivatives for
building applications, including an environmental analysis, are performed. The limitations that may
arise are examined, such as the registration of these new materials according to EU and national
regulations. Knowing the above components, the rate of return on investment is estimated and the first
conclusions for the undertaking of this investment are drawn, offering as well high environmental
benefits to the construction industry. From market analyses performed, it was suggested that the target
products (i.e., the RHA-derivatives) at an order of increasing price have as follows:
1. Production of tundish powder / insulator for steel industry (70-140 /t)

2. Production of pozzolanic material for construction industry (300-420 /t)
RHA costs already about -40 /t for handling and safe disposal, thus the finding of a valorisation
solution, viable, and possibly profitable is obligatory. In a Greek rice industrys premises, already
there are some husk burners for steam production. A certain upgrade and re-arrangement is required
for RHA enhancement in order to meet the technical requirements for insulator and pozzolan
production. The idea is to use these units both for insulation materials production as well as for the
production of pozzolanic materials; it is thus an advanced unit that involves a milling line.
For the case of insulation materials production the development of upgraded and standardized RHA as
insulator /tundish powder for steel industries, insulation panel constructors, etc., ensures viability and
remarkable profits. The best choice seems to be to produce RHA for the steel industry as this requires
no significant boiler modifications and attracts a high price. However growth in the market for RHA to
the steel market is limited. Growth in the market for RHA in the cement industry appears to be
growing and is potentially very large. A new entrant to the market place may prefer to target the
somewhat less high returns but better longer term prospects of the cement market.
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In the case of RHA conversion to pozzolanic material for building applications, the revenues of this
enterprise are higher than the operational costs leaving a net profit of 60,000 euro/y for a pozzolanic
material production of 1000 t/y and a positive return on investment of 17%. The break-even point for
this production is about 530 t/y (but production rate greater than 700 t/y is recommended), whereas
when the production approaches 4000 t/y a much higher return on investment of 57% is estimated (net
profits of 470,000 euros).
In addition, experimental verification of the derived RHA as pozzolanic materials was performed.
Contrary to most studies available, RHAs not prior treated, with a mean particle diameter of 70
microns were used as cement replacements. The aim was to assess their influence on mechanical and
durability properties of cement-based mortars. Even though their mechanical pre-treatment has been
shown to upgrade basic properties of the final product, it remains of interest to determine the
respective RHA contribution in the absence of a preparation that is energy demanding (i.e. grinding or
classifying). Major conclusions are as follows:
Untreated RHAs exhibit pozzolanicity due to their siliceous character which is almost entirely
(90%) amorphous. It is low, compared to commonly used treated-SCMs. Despite its porous
nature, untreated RHA does not increase appreciably the water requirement of cement for the
same consistency. This is important for concrete applications since it wont compromise
strength development.
Untreated RHA exhibits a late-strength gain that reaches approximately 4 MPa. This is
acceptable considering that the respective gain for a very reactive, extremely fine SCM (silica
fume) is 10 MPa. Its efficiency was measured in the area of 0.5-0.6; that practically means
that if added to concrete without prior grinding it could not replace more than half of the
selected dosages (approx. 5%) for sustaining the non-RHA performance. A previously
reported theoretical expression linking k-value with active silica ratio was not validated for
untreated RHA. Modifications are required for untreated SCMs.
Despite the high chemical reactivity of untreated RHA (about 90%), the lack of adequate
specific surface slows down their engagement in hydration reactions. Both non evaporable
water content and strength results indicate an advantage of higher quality RHA (A) at later
ages.
Untreated RHA significantly aids sorptivity of mortar. Increases of up to 50% were achieved
for 15% RHA incorporation. Performance increases with higher RHA inclusion exceeding
even the water resistance of SF-based system. Given the coarse nature of the RHAs, the
improved water resistance cannot be attributed to the pore filling effect but rather on the
inherent water repellency of the RHA. It is not clear whether this is due to the hydrophobic
nature of carbonaceous residues that are present in the ash. Resistivity was also found to be
similar to the control specimen.
187
J.G. Tapali
On the contrary, the coarse nature of untreated RHA affects resistance against chloride
penetration and - mainly - carbonation. When 15% of untreated RHA was used, carbonation
depth was almost doubled. Being pozzolanic, RHAs consume Ca(OH)2 which reduces
alkalinity and increases the rate of carbonation. This is the case for SF as well. In addition,
slow pozzolanic evolution of coarse RHA does not allow a quick and substantial formation of
secondary hydration products that could assist pores closing, thus enhanced carbonation
resistance.
By performing an overall assessment of the use of RHA in concrete, it was found that the RHA (alone
or as a mixture with calcareous fly ash) can improve significantly mechanical and durability
characteristics, decreasing as well the environmental cost of concrete production.
In general, the present Thesis contributes to the evaluation of the environmental cost of each
component of concrete and provides the best possible mix design configuration (by means of a holistic
analytical software tool) in terms of low environmental cost and fulfilling strength and durability
requirements. However, further research is required in these topics and some main suggestions for
future work include:
Estimation of the environmental cost of other construction materials except concrete
components (steel, ceramics, various mortars, aluminium, wood, plastic, glass, etc.) that are
used in the construction and structures: In this way, the total fixed environmental cost could be
assessed.
Estimation of the environmental cost during the use of the building or the structure (CO2,
emission, grey energy consumption, etc.): In this way, the total operational environmental
cost could be assessed.
By having both, total fixed environmental cost & total operational environmental cost, the
total capitalized environmental cost could be assessed, permitting a more global optimization.
In addition, the study of other new SCMs (new biomass ashes & new industrial by-products)
or the upgrading of existing SCMs, and their extended use in construction could further
enhance the environmental profile of structures in practice.
From the above conclusions from all Chapters of the present thesis, a more general conclusion can be
derived. Governments should give financial and legislative incentives to manufactures and industries
and urge them to apply new methods and a more sustainable technology. There are many different
ways for the reduction of CO2 emissions due to building industry. The methodology presented in this
study can forward the development of new policies in the construction industry and the adoption by
engineers and technicians of a sustainable perception for designing reinforced concrete structures. A
characteristic phrase of Henri David Thoreau summarizes all mentioned above: What's the use of a
fine house if you haven't got a tolerable planet to put it on?
188
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PhD Dissertation
Curriculum Vitae
Personal information
First name / Surname Julia G. Tapali
Address A. Papanastasiou str. 11A, Zip Code: 57001, Thessaloniki (Greece)
Telephone +30 6947905220
E-mail j.tapali@gmail.com
Nationality Greek
Date of birth 10 November 1981
Gender Female
Work experience
Dates 20 December 2012 - present
Occupation or position held Transport engineer
Main activities and responsibilities Participation in SEE project ADB Adriatic Danube Black Sea
Multiplatform
Name and address of employer ELKE AUTH
3rd Septemvriou, GR 54636, Thessaloniki, Greece
Type of business or sector Research - Multimodal Freight Transport
Dates 20 November 2007 - 30 September 2008

Occupation or position held Civil engineer
Name and address of employer EKTE ATEVE
26th ktovriou 42,GR 54627, Thessaloniki, Greece
Type of business or sector Steel Structures
Dates 01 January 2007 - 31 December 2007

Occupation or position held Employee
Name and address of employer SA
Ermou 42, GR 54624, Thessaloniki, Greece
Type of business or sector Telecommunications
Education and training

Dates 2011 - present
Title of qualification awarded PhD candidate
Thesis title: An integrated design process for durable concrete structures

at the minimum environmental cost Application with the incorporation of
rice husk ash
Supervisor: Assoc. Prof. Vagelis G. Papadakis
201
J.G. Tapali
Principal subjects / occupational skills Environmental footprint

covered Sustainable concrete mix design
Use of supplementary cementing materials (SCM) and especially
biomass ashes & rice husk ash
Level in national or international Higher education / University

classification
Name and type of organisation Department of Environmental and Natural Resources Management,
providing education and training School of Engineering, University of Patras, Greece.
Dates 2008 -2009

Title of qualification awarded Master Degree in Design, Organization and Management of Transport
Systems
Principal subjects / occupational skills Transportation Planning, Logistics, Freight Forwarding
covered During my Master's program I have elaborated my diploma thesis
with my supervisor Prof. Evangelos Sambrakos, Professor of
Economics at the University of Piraeus, entitled: FUNDING FOR
GREEK AND GREEK OWNED SHIPPING COMPANIES
Name and type of organisation Aristotle University of Thessaloniki
providing education and training
classification
Dates 2000 - 2007

Title of qualification awarded Civil Engineer
Principal subjects / occupational skills Reinforced concrete and steel constructions, Geotechnical
covered Works, Plumbing Projects
During my graduate studies I have elaborated my diploma
thesis under the supervision of Mrs Glykeria Kalfakakou,
Professor at Aristotle University of Thessaloniki, entitled
PUBLIC-PRIVATE PARTNERSHIPS (PPPs) -
PRESENTATION OF CASE ZEP AT KOZANI.
Name and type of organisation Aristotle University of Thessaloniki

providing education and training
classification
Personal skills and

competences
Mother tongue(s) Greek
Other language(s)
Self-assessment Understanding Speaking Writing

European level (*) Listening Reading Spoken Spoken
interaction production
English C2
Proficient
C2
Proficient
C2
Proficient
C2
Proficient
C2
Proficient
user user user user user
French A1
Basic
A1
Basic
A1 Basic User A1
Basic
A1
Basic
User User User User
202
PhD Dissertation
Computer skills and competences I hold a certificate of computer skills. I work every day using a computer and
I have also experience of web (internet) and programs such as:
Text editor - spreadsheets (Microsoft Office: Word, Excel)
Software for transportation planning, traffic simulation and GIS

(SATURN, ArcGIS)
Software application for Design (AutoCAD)
Static Programs (SAP, INSTANT)
Program of statistical analysis (SPSS)
Artistic skills and competences I enjoy drawing and reading history of art.
Driving licence(s) B
Additional Information
SEMINARS WORKSHOPS
Conference: Renewal and expansion of the rail network.
Seminar in FREIGHT AND LOGISTICS: Organization and Design of

Freight Centres.
Seminar: Organization and Management of Air Transport and

Airports.
5th International Congress on Transportation Research (September

2010, Volos, Greece).
EVIPAR: 3rd National Conference on the use of industrial by-products

in construction (24-25 September 2012, Thessaloniki, Greece).
EUROCOALASH Conference (25-27 September 2012, Thessaloniki,

Greece).
203
J.G. Tapali
RESEARCH PUBLICATIONS AND PRESENTATIONS FROM THE PRESENT THESIS
A. Publications in International Journals

1. Antiohos, S.K., J.G. Tapali, M. Zervaki, J. Sousa-Coutinho, S. Tsimas, and V.G. Papadakis, "Low-
embodied energy cement containing untreated RHA: A strength development and durability
study", Construction and Building Materials, 49, 455-463 (2013).
2. Tapali, J.G., S. Demis, and V.G. Papadakis, "Sustainable concrete mix design for a target strength
and service life", Computers & Concrete, 12(6), 377-392 (2013).
3. Demis, S., J.G. Tapali, and V.G. Papadakis, "An Investigation of the Effectiveness of the
Utilization of Biomass Ashes as Pozzolanic Materials", Construction and Building Materials, 68,
291-300 (2014).
4. Tapali, J.G., S. Demis, and V.G. Papadakis, "Plant design & economics of rice husk ash
exploitation as pozzolanic material", Waste & Biomass Valorization, accepted (2014).
B. Presentations in International Conferences with Reviewers

1. Tapali, J.G., S. Demis and V.G. Papadakis, "Use of new industrial by-products and mixtures for
reducing the environmental cost of constructions", EUROCOALASH 2012 Conference,
Thessaloniki, Greece, September 25-27, 2012.
2. Tapali, J. and V.G. Papadakis, "An optimum design of reinforced concrete structures for
prolongation of service life time at the lowest environmental cost", 3rd International Symposium on
Life-Cycle Civil Engineering (IALCCE 2012), Vienna, Austria, 3-6 October, 2012.
3. Tapali, J. and V.G. Papadakis, "Plant design & economics for rice husk ash exploitation as
pozzolanic material", SYMBIOSIS Conference, Athens, Greece, 19-21 June, 2014.
4. Tapali, J. and V.G. Papadakis, "Exlpoitation of rice husk ash as a pozzolanic material for the
construction industry", 4th International Conference on Industrial and Hazardous Waste
Management (Crete 2014), Chania, Greece, 2-5 September 2014.
C. Presentations in Greek Conferences with Reviewers

1. , ., . , . , J. Sousa-Coutinho, .. , .. ,
&
, 3
, , , 24-25/9/2012.
2. , .., . , .. , , &
, 9
, , 23-25/5/2013.
204

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Department of Environmental and Natural Resources Management

AN INTEGRATED DESIGN PROCESS FOR

Supervisor: Assoc. Prof. Vagelis G. Papadakis

Agrinio, Greece, 2014

J.G. Tapali & University of Patras

First published 2014

2. DURABILITY & SUSTAINABILITY OF CONCRETE CONSTRUCTIONS 45

2.3.1 Constituent materials for concrete composition 54

3. ENVIRONMENTAL COST OF CONCRETE PRODUCTION

4. INVESTIGATION ON THE EFFECTIVENESS OF BIOMASS ASHES

5. UTILIZATION OF RICE HUSK ASH IN THE BUILDING SECTOR

ENVIRONMENTAL BENEFITS 117

CURRICULUM VITAE 201

1.1 Brief description of the building sector

Construction in Europe (construction market forecasting network EUROCONSTRUCT 2013)

Figure 1.2 Forecast for concrete consumption up to 2100 (WBCSD 2009).

1.2 Environmental impacts of the building sector

The construction activity is a major contributor to environmental pollution and especially to

1.2.1 Environmental cost components

The main sources of GHG emissions in building construction therefore are:

b) Energy consumption of construction equipment

c) Energy consumption for processing resources

d) Disposal of construction waste

Table 1.1 Criteria for a sustainable construction project.

DESIGN CONSTRUCTION USE

1.2.2 Environmental impact of building materials

1.2.3 Reduction of the environmental cost

1. To replace as much Portland cement as possible by supplementary cementitious materials

Ground granulated blast furnace slag (GGBFS)

1.2.4 Towards a sustainable construction

Legal requirements on environmental protection

Applying environmentally friendly technology

1. Thermal and electric efficiency

Figure 1.9 Fuel consumption in the EU-25 (EC DG Env. 2004).

1.3 Objectives and structure of the present thesis

1.3.1 Objectives of the present thesis

- estimating the overall fixed environmental cost of materials

Alternative Fuels Biomass,

Rice Husk Ash Paper Sludge

1.3.2 Innovative aspects of the thesis

A structured framework of analytical methodologies, as an Integrated Design Tool, in evaluating in a

1.3.3 Structure of the thesis

Chapter 2. Durability & sustainability of concrete

initial (good quality)

initial (medium quality)

minimum acceptable limit

2.2 Concrete durability and the EN 206 approach

2.2.1 Limiting values for concrete composition

2.2.2 Performance-related design methods

The requirements related to exposure classes may be established by using performance-related

A general guidance and some applications are given:

- a service life significantly differing from 50 years is required;

- significant populations or similar structures, or elements, are to be built;

The performance-related methods that may be used include:

2.3 Concrete mix design

2.3.1 Constituent materials for concrete composition

A main constituent is a specially selected inorganic material in a proportion exceeding 5% by mass

Table 2.1 Types of common cements according to European Standard EN 197-1*.

Main Nota- Main constituents** Minor

Regarding durability requirements it is stated that, in many applications, particularly in severe

- nearly inert additions (type I)

- normal and heavy-weight aggregates conforming to EN 12620. Normal-weight aggregate has

- light-weight aggregates conforming to EN 13055-1. Light-weight aggregate of mineral origin